CN1289157C - Biomedical devices containing internal wetting agents - Google Patents

Abstract

This invention includes a wettable silicone hydrogel comprising the reaction product of a least one silixane containing macromer; at least one high molecular weight hydrophilic polymer; and at least one comptabilizing component as well as contact lens, medical devices and methods of obtaining such products.

Description

The bio-medical instrument that contains internal wetting agents

Related application

The series number that present patent application requirement calendar year 2001 JIUYUE was submitted on the 10th is 60/318,536 U.S. Provisional Application No..

Invention field

The present invention relates to contain the silicon hydrogel of internal wetting agents, with and its production and use.

Background of invention

Since nineteen fifties, improved vision at least at the commercial contact lens that used.The first secondary contact lens is made by hard material, thereby more or less not too comfortable for the user.Developed at present novel eyeglass, they are with softer material, hydrogel normally, and especially silicon hydrogel is made.Silicon hydrogel is the water swellable polymer network, and they have high oxygen permeability, and it is hydrophobicity rather than hydrophilic that the surface mostly is.These eyeglasses provide good comfort level for many bespectacled people, but some users over-drastic eyes scale that but can not feel like oneself, and have when using these eyeglasses is arranged, and cause visual acuity to reduce.Thisly do not accommodate that scale has been considered to be caused by the hydrophobic characteristics of lens surface and the interaction between those hydrophilic surfaces that has protein, lipid and mucinous surface and eyes.

Also the someone attempts by relaxing this problem with the surface of hydrophilic coating coating silicon hydrogel contact lens.For example, the someone discloses by apply plasma coating on lens surface and can make the silicone hydrogel lens more compatible with ocular surface.But also nobody openly has the uncoated silicone hydrogel lens of low surface deposits incidence rate.

The someone discloses and introduced inner hydrophilic reagent (perhaps wetting agent) in the reactant mixture that contains macromonomer.But, be not that all macromonomers that contains silicone all demonstrate the compatibility with hydrophilic polymer.Also the someone discloses by add polymerizable surfactants in the monomer mixture that is used to form goods modification has been carried out on the surface of polymer product.But, this can not support in the improvement of wettability and the minimizing of surface deposits.

There has been the people that polyvinylpyrrolidone (PVP) or poly--2-ethyl-2- azoles quinoline are joined the perforation network that demonstrates low surface friction degree, low dehydration rate and Gao Nai biogenic deposit degree in the hydrogel composition in order to formation.But disclosed aqueogel is conventional hydrogel, and does not have openly how to import hydrophobic components under the situation of not losing mhc monomer, such as siloxanyl monomers.

Though heavy polymer might be imported in the silicone hydrogel lens as internal wetting agents, this polymer is difficult to be dissolved in the reactant mixture that contains silicone.In order to dissolve these wetting agent, must use silicone macromonomer or other prepolymers.These silicone macromonomers or prepolymer must prepare in dividing other step and and then mix with the residual components of silicon hydrogel preparation then.This extra step (perhaps a plurality of step) can increase cost and the time that these eyeglasses of preparation need spend.

Therefore, find that a kind of not need to use surface treatment that the eyeglass prescription of wettability and anti-surface deposition just can be provided will be useful on eyes.

Summary of the invention

The present invention relates to a kind of wettable silicon hydrogel, it comprises at least a macromonomer that contains siloxanes; At least a high molecular hydrophilic polymer; Product with at least a compatible components.

The invention still further relates to a kind of method, it comprises the steps: that (a) will contain at least a high molecular hydrophilic polymer, the reactive component of at least a compatible components of at least a macromonomer that contains siloxanes and effective dose mix and (b) product of curing schedule (a) to form bio-medical instrument.

The invention still further relates to a kind of method, its reactive component that comprises the steps: that (a) will contain the compatible components of high molecular hydrophilic polymer and effective dose mix and (b) at the product of minimum gelling time or above time point curing schedule (a) to form wettable bio-medical instrument.

The present invention also further relates to a kind of ophthalmic lens that contains silicon hydrogel, and it is not carrying out under the surface-treated situation, has the tear film splitting time at least about 7 seconds.

The present invention further relates to a kind of silicon hydrogel contact lens, it comprises the permeable component of at least a oxygen, at least a compatible components and an amount of high molecular hydrophilic polymer, the amount of described high molecular hydrophilic polymer is enough to make described device not carrying out under the surface-treated situation, has the tear film splitting time at least about 7 seconds after wearing with about one day.

A kind of device that contains the silicon hydrogel contact lens, surface deposition can not take place in basically under the situation of not carrying out surface modification.

Detailed Description Of The Invention

Bio-medical instrument is formed by reactant mixture, this reactant mixture comprises, basically by or form by the compatible components of the macromonomer that contains siloxanes, at least a high molecular hydrophilic polymer and compatible amount.

Be surprised to find, under the situation of not carrying out surface modification, have in the remarkable body or bio-medical instrument, the especially Ophthalmoligic instrument of clinical wettability can be by comprising effective dose in the silicon hydrogel preparation high molecular hydrophilic polymer and the compatible components of compatible amount prepare.Remarkable wettability is meant with the similar formulations that does not contain any hydrophilic polymer to be compared, and the dynamic contact angle that advances reduces at least about 10%, preferably at least about 20%, in certain embodiments at least about 50%.Before the present invention, the Ophthalmoligic instrument that forms by silicon hydrogel or have to carry out surface modification clinical wettability to be provided or to form by at least a macromonomer that comprises silicone with hydroxy functionality.

" bio-medical instrument " used herein be meant and be designed for, though or mammalian tissues or liquid internal or on, preferably be used on people's tissue or the liquid or within any goods.The example of these devices is including, but not limited to conduit, implant, and metal stent and Ophthalmoligic instrument are such as intraocular lens and contact lens.Preferred bio-medical instrument is an Ophthalmoligic instrument, especially contact lens, the most particularly contact lens of being made by silicon hydrogel.

Term used herein " eyeglass " and " Ophthalmoligic instrument " refer to and are present in the eyes or the device on the eyes.These devices can provide vision correction, wound care, dispenser, the combination of diagnostic function or enhancing or realization dressing effect or these characteristics.Term " eyeglass " is including, but not limited to soft contact lens, hard contact lens, and intraocular lens is pressed in the eyeglass above the eyes, ocular implant and optics implant.

Term used herein " monomer " is meant the chemical compound that contains at least a polymerizable groups, and its mean molecule quantity is less than about 2000 dalton when measuring by the gel permeation chromatography refractometry.Therefore, monomer comprises dimer, also comprises oligomer sometimes, comprises the oligomer that is formed by more than one monomeric unit.

The meaning that phrase used herein " does not carry out surface treatment " is that the outer surface of apparatus of the present invention is not handled separately to improve the wettability of described device.Because the processing that the present invention can carry out in advance comprises Cement Composite Treated by Plasma, grafting, coating etc.But, can apply some coatings to device of the present invention, these coatings also can provide other characteristic except that the wettability that improves, such as, but not limited to antimicrobial coating.

Various molecular weight ranges are disclosed among the present invention.For chemical compound with isolated molecular structure, the molecular weight of reporting among the present invention be with the molecular formula be basic calculation and with gram/reported in mole.For polymer, molecular weight (number average) be measure by the gel permeation chromatography refractometry and be the unit report with dalton, perhaps as John Wiley ﹠amp; The Encyclopedia of Polymer Science and Engineering that Sons company publishes, N-VinylAmide Polymers, second edition, the 17th volume, the 198-257 page or leaf is described, reports by dynamic viscosity measurement method mensuration and with the K-value.

The high molecular hydrophilic polymer

" high molecular hydrophilic polymer " used herein is meant that weight average molecular weight is not less than about 100,000 daltonian materials, and wherein said material can improve the wettability of solidified silicon hydrogel in being incorporated into the silicon hydrogel preparation time.The preferred weight average molecular weight of these high molecular hydrophilic polymeies is greater than about 150,000 dalton; More preferably from about 150, about 2,000,000 dalton of 000-, also more preferably from about 300, about 1,800,000 dalton of 000-, most preferably from about 500, about 1,500,000 dalton of 000-(all be weight average molecular weight).

Perhaps, the molecular weight of hydrophilic polymer of the present invention also can be as John Wiley ﹠amp; The Encyclopedia of Polymer Science and Engineering that Sons company publishes, N-VinylAmide Polymers, second edition, the 17th volume, the 198-257 page or leaf is described, measures according to the dynamic viscosity measurement method, with the K-value representation.When expressing in this way, the K value of hydrophilic monomer is greater than about 46, preferably between about 46-about 150.The amount of high molecular hydrophilic polymer in the preparation of these devices is enough to make contact lens to remain essentially under the situation of not carrying out surface modification surface deposition does not take place in the use.Typical life cycle comprised at least about 8 hours, preferably wore several days continuously, did not more preferably extract and wore 24 hours or the longer time.Basically do not have the surface deposition meaning to refer to that when watching with corneal microscope, the patient wears to be had in the eyeglass at least about 80%, preferably at least about 90%, more preferably from about 100% be considered to do not demonstrate or only demonstrate slight deposition wearing with the cycle.

The high molecular hydrophilic polymer of appropriate amount comprises about 15wt% in the about 1-of the gross weight of total overall reaction component, the more preferably from about about 15wt% of 3-, the most preferably from about about 12wt% of 5-.

The example of high molecular hydrophilic polymer is including, but not limited to polyamide, polylactone, polyimides, poly-lactam and functionalized polyamide, polylactone, polyimides, poly-lactam, such as the monomer such as the HEMA copolymerization of the hydroxy functional groups by making DMA and less mole, make the hydroxyl and the material that contains polymerizable groups of gained copolymer then, as methacrylic acid isocyanato ethyl or methacrylic chloride reaction and functionalized DMA.Also can use the hydrophilicity prepolymer that forms by DMA or N-vinyl pyrrolidone and glycidyl methacrylate.The glycidyl methacrylate ring can be opened the formation glycol, and the hydrophilicity prepolymer that it can be used for connecting other in hybrid system is with the monomer that increases the functionalized silicone of high molecular hydrophilic polymer, hydroxyl and the compatibility between any other group of giving the compatibility.Preferred high molecular hydrophilic polymer is to comprise annulus in its skeleton, more preferably those polymer of cyclic amides or cyclic imides.The high molecular hydrophilic polymer is including, but not limited to the poly-N-vinyl ketopyrrolidine, poly-N-vinyl-2-piperidones, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidones, poly-N-vinyl-4-methyl-2-piperidones, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-Pyrrolidone, polyvinyl imidazol, poly--N, the N-DMAA, polyvinyl alcohol, polyacrylic acid, polyethylene glycol oxide, poly--2-ethyl- azoles quinoline, heparin polysaccharide, polysaccharide, its mixture and copolymer (comprise block or random, side chain, multichain, the copolymer of comb shape or star), wherein especially preferred poly-N-vinyl ketopyrrolidine (PVP).Also can use copolymer, such as the graft copolymer of PVP.

The high molecular hydrophilic polymer provides the interior wettability of wettability, the especially body of Gai Shaning of improvement for medical devices of the present invention.Be not entangled in any theory, we believe that the high molecular hydrophilic polymer is the hydrogen bond receiver, and it forms hydrogen bond with water in water environment, thereby it is more hydrophilic to become effectively.Do not exist water can promote that hydrophilic polymer imports in the reactant mixture.Except the high molecular hydrophilic polymer of enumerating especially, estimate that any high molecular polymer all will can be used among the present invention, condition is when described polymer joins in the silicon hydrogel preparation, and hydrophilic polymer (a) is not separated with reactant mixture basically and (b) makes the gained cured polymer have wettability.In certain embodiments, preferred high molecular hydrophilic polymer dissolves in the diluent under processing temperature.May preferably make the manufacturing process of water or water-soluble diluent, this is because they are simple and with low cost.In these embodiments, preferred water-soluble high molecular hydrophilic polymer under processing temperature.

Compatible components

" compatible components " used herein is meant that number-average molecular weight is less than about 5000 dalton, preferably is lower than about 3000 dalton, and comprises the chemical compound of at least one polymerizable groups, and it can make selected reactive component solubilising.Do not have compatible components, the permeable component of high molecular hydrophilic polymer and oxygen just can not be fully miscible, and can not use rational processing conditions to form optically transparent Ophthalmoligic instrument.Compatible components of the present invention is by permeable component of dissolved oxygen and high molecular hydrophilic polymeies such as hydrogen bond action, dispersion force, its combinations.Therefore, can all can be used as compatible components with any functional material of any mode and hydrophilic polymer reaction.Also can use macromonomer (number-average molecular weight is about 15,000 dalton of about 5000-), as long as they have the compatible function of describing among the present invention.If use compatible macromonomer, then may still essentially add the wettability of extra compatible components in the gained Ophthalmoligic instrument, to obtain to wish.

The compatible components of the present invention that one class is suitable comprises at least one reactive hydrogen and at least one siloxane group.Reactive hydrogen can be by any hydrophilic monomer bonding of hydrogen bond and hydrophilic polymer and existence.Hydroxyl is easy to participate in hydrogen bond action, is a kind of preferred source of reactive hydrogen therefore.Therefore, in one embodiment, compatible components of the present invention advantageously comprises at least one hydroxyl and at least one " Si-O-Si-" group.The oxygen that preferred silicone is connected with it accounts for more than about 10wt% of described compatible components, more preferably from about more than the 20wt%.

The ratio of Si and OH can provide the compatible components no less important of the compatible degree of hope in the compatible components for acquisition.If hydrophobicity part is too high with the ratio of OH, then compatible components makes the hydrophilic polymer may be poor aspect compatible, thereby causes producing inconsistent reactant mixture.Therefore, in certain embodiments, the ratio of Si and OH is lower than about 15: 1, and preferred about 1: about 10: 1 of 1-.In certain embodiments, compare with secondary alcohol, primary alconol can provide the improved compatibility.It will be understood to those of skill in the art that the amount of compatible components and select to depend on that the wettability for obtaining to wish needs how many hydrophilic polymeies and siliceous one monomers and the inconsistent degree of hydrophilic polymer.

The example of compatible components comprises the monomer of formula I and II:

Wherein: n is the integer between the 3-35, preferred 4-25;

R¹Be hydrogen, C_1-6Alkyl;

R², R³And R⁴Be C independently_1-6Alkyl, three C_1-6Alkyl siloxy, phenyl, naphthyl, the C of replacement_1-6Alkyl, the phenyl of replacement, the perhaps naphthyl of Qu Daiing,

Wherein alkyl substituent is selected from following one or more: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl, wherein aromatic substituent is selected from following one or more: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl;

R⁵Be hydroxyl, contain the alkyl of one or more hydroxyls, perhaps (CH₂(CR⁹R¹⁰)_yO)_x)-R¹¹, wherein y is 1-5, preferred 1-3, and x is the integer of 1-100, preferred 2-90, more preferably 10-25; R⁹-R¹¹Be independently selected from H, have the alkyl of maximum 10 carbon atoms and the alkyl that is replaced by at least one polar functional group with maximum 10 carbon atoms;

R⁶It is the divalent group that contains maximum 20 carbon atoms;

R⁷It is the univalent perssad that can carry out maximum 20 carbon atoms of containing of free radical and/or cationic polymerization; With

R⁸Be bivalence or the trivalent group that contains maximum 20 carbon atoms.

Reactant mixture of the present invention can comprise more than one compatible components.

For the compatible components of simple function group, preferred R¹Be hydrogen, preferred R², R³And R⁴Be C_1-6Alkyl and three C_1-6Alkyl siloxy, most preferable and trimethylsiloxy.For multi-functional (difunctional or more multi-functional) compatible components, R¹-R⁴Comprise olefinic unsaturated polymerizable group independently, more preferably comprise acrylate, styryl, acrylic acid C_1-6Arrcostab, acrylamide, C_1-6Alkyl acrylamide, N-vinyl lactam, N-vinylamide, C_2-12Thiazolinyl, C_2-12Thiazolinyl phenyl, C_2-12Thiazolinyl naphthyl or C_2-6Thiazolinyl phenyl C_1-6Alkyl.

Preferred R⁵Be hydroxyl ,-CH₂OH or CH₂CHOHCH₂OH, wherein hydroxyl most preferably.

Preferred R⁶Be bivalence C_1-6Alkyl, C_1-6Alkoxyl, C_1-6Alkoxy C_1-6Alkyl, phenylene, naphthylene, C_1-12Cycloalkyl, C_1-6Alkoxy carbonyl, amide groups, carboxyl, C_1-6Alkyl-carbonyl, carbonyl, C_1-6Alkoxyl, the C of replacement_1-6Alkyl, the C of replacement_1-6Alkoxyl, the C of replacement_1-6Alkoxy C_1-6Alkyl, the phenylene of replacement, the naphthylene of replacement, the C of replacement_1-12Cycloalkyl, wherein said substituent group are selected from one or more in the following stated group: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl.Particularly preferred R⁶Be bivalence methyl (methylene).

Preferred R⁷Comprise the free radical activity group, such as acrylate, styryl, vinyl, vinyl ethers, itaconic acid ester group, acrylic acid C_1-6Arrcostab, acrylamide, C_1-6Alkyl acrylamide, N-vinyl lactam, N-vinylamide, C_2-12Thiazolinyl, C_2-12The thiazolinyl phenyl, C_2-12Thiazolinyl naphthyl, perhaps C_2-6Thiazolinyl phenyl C_1-6Alkyl or cation activity group are such as vinyl ethers or epoxide group.Particularly preferred R⁷It is methacrylate.

Preferred R⁸Be bivalence C_1-6Alkyl, C_1-6Alkoxyl, C_1-6Alkoxy C_1-6Alkyl, phenylene, naphthylene, C_1-12Cycloalkyl, C_1-6Alkoxy carbonyl, amide groups, carboxyl, C_1-6Alkyl-carbonyl, carbonyl, C_1-6Alkoxyl, the C of replacement_1-6Alkyl, the C of replacement_1-6Alkoxyl, the C of replacement_1-6Alkoxy C_1-6Alkyl, the phenylene of replacement, the naphthylene of replacement, the C of replacement_1-12Cycloalkyl,, wherein said substituent group is selected from one or more in the following stated group: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl.Particularly preferred R⁸Be C_1-6Alkoxy C_1-6Alkyl.

The example of the compatible components of particularly preferred formula I is the acrylic acid 2-methyl of 2--2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-(trimethyl silyl) oxygen] the disiloxane base] propoxyl group] propyl ester (can also two (trimethylsiloxy) methyl-monosilanes of called after (3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group.

Above chemical compound, two (trimethylsiloxy) methyl-monosilanes of (3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group are formed by epoxide, and it obtains is chemical compound shown in above and 80: 20 the mixture of (2-methacryloxypropyl-3-hydroxyl propoxyl group) propyl group pair (trimethylsiloxy) methyl-monosilanes.In the present invention, described 80: 20 mixture will be more preferably than two (trimethylsiloxy) methyl-monosilanes of pure (3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group.In certain embodiments of the invention, preferably there is a certain amount of primary hydroxyl, is preferably greater than about 10wt%, more preferably at least about 20wt%.

The monomer that contains silicone of the hydroxy-functional that other are suitable comprises (3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group three (trimethylsiloxy) silane:

Two-the 3-methacryloxypropyl-2-hydroxypropyl oxygen propyl group polydimethylsiloxane

3-methacryloxypropyl-2-(2-hydroxy ethoxy) propyl group oxygen) two (trimethylsiloxy) methyl-monosilanes of propyl group

N-2-methylacryoyloxyethyl-O-(methyl-two-trimethylsiloxy-3-propyl group) silicyl carbamate

N, N, N ', N '-four (3-methacryloxypropyl-2-hydroxypropyl)-α, α-two-3-aminopropyl-polydimethylsiloxane

Glycidyl methacrylate also can be used as compatible components with the product that contains the polydimethylsiloxane of amido functional group.Other suitable compatible components comprise United States Patent (USP) 5,994, those disclosed and United States Patent (USP) 4,259,467 in 488 the 6th, 7 and 8 hurdles; 4,260,725; 4,261,875; 4,649,184; 4,139,513; 4,139,692; US 2002/0016383; Disclosed monomer in 4,139,513 and 4,139,692.Be incorporated herein by reference in this these and any other the patent or application of quoting.

The other structure that can be used as suitable compatible components comprises and is similar to Pro.ACS Dlv.Polym.Mat.Sci.Eng., April 13-17, and those of disclosed chemical compound in 1997,42 pages, it has following structure:

Wherein, n=1-50, R comprise H or polymerisable unsaturated group independently, and at least one R comprises polymerisable group, at least one R, and preferred 3-8 R comprises H.

The compatible components that second class is suitable comprises those with structure shown in the following formula III:

IWA-HB-[IWA-HB]_X-IWA

Wherein x is 1-10;

IWA is with undefined difunctional hydrophilic polymer, but its number-average molecular weight is about 50,000 dalton of about 1000-; With

HB is the difunctional segment that contains at least one N, and described N can form hydrogen bond with the reactive hydrogen that hydrophilic polymer and any other contain in the component of reactive hydrogen.

Preferred IWA group can derived from alpha, and the PVP of ω-hydroxy-end capped and number-average molecular weight are about 1,000-about 50,000 daltonian α, ω-hydroxy-end capped polyoxyalkylene glycol.

Preferred HB group comprises the amide of difunctional, acid imide, carbamate and urea, its combination etc.

The compatible components of formula III can be by making the end capped polyoxyalkylene glycol of amine (Jeffamines) and isocyanates, carbonochloridic acid ester or acyl chlorides or anhydride reaction preparation.

Suitable in addition compatible components is referring to United States Patent (USP) 4,235,985, and it is hereby incorporated by.

Suitable compatible components also can comprise has carried out modification so that it has the macromonomer that contains silicone of compatible function as defined above.This macromonomer comprises a considerable amount of group or the reactive hydrogen functional groups that Si and HB are arranged as defined above simultaneously, such as hydroxyl.The macromonomer that one class is suitable comprises the macromonomer by the hydroxy-functional of group transfer polymerization (GTP) preparation, the perhaps functionalized prepolymer of styrene of the methacrylate of hydroxy functional groups and silicone methacrylate, referring to United States Patent (USP) 6,367,929, it is hereby incorporated by.In the present invention, these macromonomers preferably with another kind of compatible components, use together such as the monomer that contains siloxanes.Other macromonomer, also can use independently or be used in combination such as those that prepare by radical polymerization or condensation reaction with other compatible components, as long as the Si/ hydrogen mol ratio (OH) of macromonomer is lower than about 15: 1, preferred about 1: the mol ratio of about 10: 1 of 1-or silicon/HB is lower than about 10: 1, and preferred about 1: 1-got final product in about 8: 1.But, it will be understood to those of skill in the art that to comprise that difluoro methylene reduction is provided provide the mol ratio of the compatibility.

Suitable simple function group compatible components can derive from Gelest, Inc.Morrisville, PA.Suitable polyfunctional group compatible components can derive from Gelest, Inc, Morrisville, PA or can use 5,994,488 and 5,962, the preparation of 548 disclosed methods.Suitable substance P EG type simple function group compatible components can be used disclosed method preparation among the PCT/JP02/02231.Suitable compatible macromonomer can use United States Patent (USP) 5,760, disclosed universal method preparation in 100 (substance Cs) or 6,367,929.

Be considered to be particularly suitable for being bio-medical instrument though contain the compatible components of hydroxy functional group, particularly Ophthalmoligic instrument provides compatible polymer, but any in polymerization and/or when being shaped to end article the compatible components compatible with selected hydrophilic component all can use.Compatible components can be tested in order to the bulk phase capacitive that places an order and select.In this test, with 1 gram use respectively that list-the 3-methacryloxypropyl is end capped, the end capped polydimethylsiloxane of monobutyl (mPDMS, MW are 800-1000) and monomer promptly to be tested at 1 gram 3, mix in 7-dimethyl-3-capryl alcohol under about 20 ℃.The PVP of 12 weight portion K-90 and the mixture of 60 weight portion DMA under agitation are added drop-wise in the solution of hydrophobic components, after solution is stirring 3 minutes, still keep muddy.Measure the PVP of adding and the amount of DMA blend, with the gram expression, record is as mhc monomer sex index.Compatibility index is greater than 0.5 gram, and more preferably greater than about 1 gram, most preferably any compatible components greater than about 1.5 grams will be suitable among the present invention.It will be understood to those of skill in the art that the molecular weight of activity compatible component will influence the result of above test.Molecular weight may need to mix long period of time to provide representational result greater than about 800 daltonian compatible components.

The compatible components of the present invention of " effective dose " is meant and need dissolves required amount with other component compatibility of high molecular hydrophilic polymer and polymer formulations or with it.Therefore, the amount of compatible components will depend on the amount of employed hydrophilic polymer to a certain extent, for compatible with the high molecular hydrophilic polymer of higher concentration, need more compatible components.The compatible components of effective dose comprises about 5% (wt% is in the gross weight of reactive component)-Yue 90% in polymer formulations, and preferably about 10%-is about 80%, and most preferably from about 20%-about 50%.

Except high molecular hydrophilic polymer and compatible components of the present invention, other hydrophilic monomer, the component of raising oxygen permeability, cross-linking agent, additive, diluent, polymerization initiator all can be used to prepare bio-medical instrument of the present invention.

The permeable component of oxygen

Compositions of the present invention and device may further include and other can make its oxygen permeability than the enhanced component of conventional hydrogel.The permeable component of suitable oxygen comprises monomer, macromonomer and the active prepolymer that contains siloxanes, the triple-linked monomer of fluorochemical monomer, macromonomer and active prepolymer and carbon containing-carbon, macromonomer and active prepolymer and combination thereof, but do not comprise described compatible components.For the purposes of the present invention, term " macromonomer " will be used for covering simultaneously macromonomer and prepolymer.The preferred permeable component of oxygen comprises the monomer that contains siloxanes, macromonomer and composition thereof.

The suitable monomer that contains siloxanes comprises, United States Patent (USP) 4, the amide analogue of the TRIS that describes in 711,943, United States Patent (USP) 5,070, vinyl carbamate or the carbonate analog described in 215 also can use United States Patent (USP) 6,020, the monomer that comprises in 445, the patent of any other that mention in above-mentioned these patents and this description all is hereby incorporated by.More particularly, 3-methacryloxypropyl three (trimethylsiloxy) silane (TRIS), the end capped polydimethylsiloxane of monomethacryloxypropterminated, polydimethylsiloxane, two (trimethylsiloxy) methyl-monosilanes of 3-methacryloxypropyl, methacryloxypropyl pentamethyl disiloxane and combination thereof can be particularly useful as the monomer that contains siloxanes of the present invention.The monomeric amount that contains siloxanes in addition can be the about 75wt% of about 0-, the more preferably from about about 60wt% of 5-, most preferably from about 10-40wt%.The amount of the permeable component of described oxygen is the about 80wt% of 0-.

The suitable macromonomer that contains siloxanes, its number-average molecular weight are about 5, about 15,000 dalton of 000-.The macromonomer that contains siloxanes comprises and contains at least one siloxane group, preferably at least one dialkyl siloxane group group, the more preferably material of at least one dimethylsiloxane group.The macromonomer that contains siloxanes can comprise other components, such as urethane groups, and alkylidene or alkylene oxide base, polyoxyalkylenes, arlydene, Arrcostab, amide groups, carbamate groups, perfluoro alkoxy, NCO, its combination etc.The siloxane macromer that contains of preferred type can be by making one or more siloxanes and one or more acrylic acid or the polymerization of methacrylic material formation.The macromonomer that contains siloxanes can pass through generations such as group transfer polymerization (" GTP "), radical polymerization, condensation reaction.According to selected component with use condition as known in the art, can in one or series of steps, form the macromonomer that contains siloxanes.The concrete macromonomer that contains siloxanes with and preparation method thereof, be included in United States Patent (USP) 5,760, in 100 as substance A-D those disclosed (methacrylate functionalized silicone-fluoro-ether urethane and methacrylate functionalized silicone urethane), with United States Patent (USP) 6, those disclosed in 367,929 (prepolymer that the styrene of the methacrylate of hydroxy functional groups and silicone methacrylate is functionalized), its disclosure is hereby incorporated by.

The suitable active prepolymer that contains siloxanes comprises that (it is disclosed in United States Patent (USP) 5 to the functionalized polydimethylsiloxane of vinyl carbamate in addition, in 070215) and the urethane groups prepolymer, this urethane groups prepolymer comprises alternative " firmly " fragment that is formed by short-chain diol and di-isocyanate reaction and is carried out α by two reactive hydrogens, ω-end capped polymer formed " soft " fragment by higher molecular weight.The instantiation of the suitable prepolymer that contains siloxanes with and preparation method thereof referring to United States Patent (USP) 5,034,461, it is hereby incorporated by.

Hydrogel of the present invention can comprise at least a macromonomer that contains siloxanes.The amount that contains the macromonomer of siloxanes can be the gross weight in reactive component, the about 50wt% of about 5-, the about 50wt% of preferably about 10-, the more preferably from about about 45wt% of 15-.

Suitable fluorochemical monomer comprises fluorine-containing (methyl) acrylate, more specifically comprises, for example, (methyl) acrylic acid fluorine-containing C₂-C₁₂Arrcostab, as 2,2, (methyl) acrylate of 2-trifluoroethyl, 2,2,2,2 ', 2 ', 2 '-(methyl) acrylate of hexafluoro isopropyl, 2,2,3,3,4,4, (methyl) acrylate of 4-seven fluorine butyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8, (methyl) acrylate of 8-15 fluorine octyl groups, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9, (methyl) acrylate of 9-ten hexafluoro nonyls etc.Fluorine-containing macromonomer and active prepolymer comprise macromonomer and the prepolymer that comprises described fluorochemical monomer.

Have now found that the wettability that contains the silicon hydrogel of macromonomer can be improved by comprising at least a hydrophilic polymer and compatible components.Improved wettability comprises that the dynamic contact angle that advances reduces at least about 10%, preferably at least about 20%, reduces at least about 50% in certain embodiments.In certain embodiments, may preferably use and contain the monomeric mixture of siloxanes or contain siloxanyl monomers and contain the macromonomer of siloxanes or the mixture of prepolymer.

Hydrophilic monomer

In addition, reactive component of the present invention also can comprise any hydrophilic monomer that is used to prepare conventional hydrogel.For example, can use and contain acrylic acid groups (CH₂=CROX, wherein R is hydrogen or C_1-6Alkyl, X are O or N) or vinyl (C=CH₂) monomer.The example of other hydrophilic monomer is a N,N-DMAA, methacrylic acid 2-hydroxyl ethyl ester, the glycerol methacrylate, the 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, the N-vinyl pyrrolidone, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide and combination thereof.

Except above-mentioned other hydrophilic monomer, can also use the polyoxyethylene alcohol how that contains the terminal hydroxy group that one or more functional groups that contained polymerizable double bond replace.The example comprises, as United States Patent (USP) 5,484, disclosed Polyethylene Glycol in 863, as United States Patent (USP) 5,690,953, United States Patent (USP) 5,304, the alkyl polyglucoside of disclosed ethoxylation in 584, and United States Patent (USP) 5, the bisphenol-A of disclosed ethoxylation in 565,539 is with a molar equivalent or the end-capping group more than the molar equivalent, as methacrylic acid isocyanatoethyl ester, methacrylic anhydride, methacrylic chloride, reactions such as vinyl benzene formyl chloride form and contain one or more passing through such as carbamate, the polyethylene that the brace scission of link of urea or ester group is incorporated into the terminal polymerizable alkylene hydrocarbyl group on the many alcohol of polyethylene is alcohol how.

Further example comprises United States Patent (USP) 5,070, disclosed hydrophilic ethylene carbonate or vinyl carbamate monomer in 215, United States Patent (USP) 4,910, disclosed hydrophilic  oxazolone monomer in 277, and dextrosan glycosides.

Preferred other hydrophilic monomer is N, N-DMAA (DMA), methacrylic acid 2-hydroxyl ethyl ester (HEMA), the glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinyl pyrrolidone (NVP), polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid and its combination, the hydrophilic monomer that comprises DMA is particularly preferred.The amount of hydrophilic monomer can be in the about 0-70wt% of the gross weight of reactive component in addition, more preferably from about the about 60wt% of 5-, most preferably from about 10-50wt%.

Cross-linking agent

Suitable cross-linking agent is the chemical compound that has two or more polymerizable functional groups.Cross-linking agent can be hydrophilic or hydrophobicity, in certain embodiments of the invention, the mixture that has been found that hydrophilic and hydrophobicity cross-linking agent can make silicon hydrogel have improved optical clarity (comparing the optical haze degree with reduction with CSI Thin Lens ).The example of suitable hydrophilic crosslinker comprises and contains two or more polymerizable functional groups, and the hydrophilic functional group, such as the chemical compound of polyethers, amide or hydroxyl.Concrete example comprises TEGDMA (tetraethylene glycol dimethacrylate, TrEGDMA (triethylene glycol dimethacrylate), ethylene glycol dimethacrylate (EGDMA), ethylenediamine DMAA, glycerol dimethylacrylate and combination thereof.The example of suitable hydrophobicity cross-linking agent comprises multi-functional compatible components, multi-functional polyethers-polydimethylsiloxaneblock block copolymers, its combination etc.Concrete hydrophobicity cross-linking agent comprise the end capped polydimethylsiloxane of acryloyl-oxy propyl group (n=10 or 20) (acPDMS), the siloxane macromer of hydroxy acrylic acid ester functional, the end capped PDMS of methacryloxypropyl, butanediol dimethylacrylate, divinylbenzene, 1,3-two (3-methacryloxypropyl) four (trimethylsiloxy) disiloxane and composition thereof.Preferred cross-linking agents comprises TEGDMA, EGDMA, acPDMS and combination thereof.The use amount of hydrophilic crosslinker is generally the about 2wt% of about 0-, the preferred about 2wt% of about 0.5-, the use amount of hydrophobicity cross-linking agent is approximately the about 5wt% of gross weight 0-in reactive component, can with mol% unit perhaps, be about 0.2 mM of about 0.01-/gram reactive component, the preferred about 0.1 mM/gram of about 0.02-, the more preferably about 0.6 mM/gram of 0.03-.

Have been found that the amount that increases cross-linking agent in the final polymer can reduce the light haze value.But about 0.15 mM/when the gram reactive component was above, modulus was increased to the level (greater than about 90psi) that is higher than common hope when crosslinker concentration is increased to.Therefore, in the present invention, the composition of cross-linking agent and the selection of consumption will make the concentration of cross-linking agent in the reactant mixture between the per 100 gram reactive components of the about 10 mM cross-linking agent of about 1-.

Also can comprise this area known other component or additive usually.Additive comprises but is not limited to ultraviolet absorption compound and monomer, reactive dye, antimicrobial compound, pigment, light-sensitive material, releasing agent, its combination etc.

Diluent

Reactive component (compatible components, hydrophilic polymer, the permeable component of oxygen, hydrophilic monomer, cross-linking agent and other components) is mixing and reaction formation reactant mixture under the situation that does not have the water existence with in the presence of the optional at least a diluent.The type of employed diluent and consumption also influence the performance of resulting polymers and goods.The optical haze degree of end article can be improved by the diluent of selecting relative hydrophobicity and/or the concentration that reduces the diluent that uses with wettability.As discussed above, the hydrophobicity that increases diluent also can be so that the component of compatibility difference (as measuring by compatibility test) be processed to form compatible polymer and goods.But when diluent becomes more hydrophobic, the procedure of processing of must water replacing diluent will need to use the solvent that is different from water.This may undesirably increase the complexity and the cost of manufacturing process.Therefore, to make component have the compatibility of hope, simultaneously the diluent of essential processing convenience be arranged again be very important in selection.The diluent that is used to prepare apparatus of the present invention comprises ether, ester, alkane, halogenated alkane, silane, amide, alcohol and combination thereof.Amide and alcohol are preferable absorbent, and the secondary and tertiary alcohol is most preferred alcohols diluent.The example that can be used as the ether of diluent of the present invention comprises oxolane, the tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, the diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene diphenate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, the dipropylene glycol methyl ether acetas, propylene glycol positive propyl ether, dipropylene glycol positive propyl ether, the tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, the propylene glycol diphenyl ether, the dipropylene glycol dimethyl ether, Polyethylene Glycol, polypropylene glycol and composition thereof.The example that can be used for ester of the present invention comprises ethyl acetate, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, isopropyl lactate.Can be used as the example that diluent is used for halogenated hydrocarbons of the present invention and comprise dichloromethane.Can be used as the example that diluent is used for silane of the present invention and comprise prestox cyclisation tetrasiloxane.

Can be used as example that diluent is used for alcohol of the present invention comprise have as shown in the formula those:

Wherein, R, R ' and R " are independently selected from H; have straight chain, side chain or the ring-type univalent alkyl of 1-10 carbon; it can be chosen wantonly by one or more groups and replace; comprise halogen, ether, ester, aryl, amino, amide, alkene, alkynes, carboxylic acid, alcohol, aldehyde, ketone etc.; " bonding forms one or more circuluses together for perhaps any two or whole three R; R ' and R, such as the alkyl that contains 1-10 carbon, it also can be substituted as described in just now, and prerequisite is R, R ' and R " in have one to be H at the most.

Preferably, R, R ' and R " are independently selected from straight chain, side chain or the cyclic alkyl of a H or the unsubstituted 1-7 of a containing carbon.More preferably R, R ' and R " are independently selected from straight chain, side chain or the cyclic alkyl of the unsubstituted 1-7 of a containing carbon.In certain embodiments, preferable absorbent contain altogether 4 or more than, more preferably 5 or above carbon atom because the molecular weight of diluent is high more, its volatility is low more, inflammability is low more.Work as R, R ' and R " in one when being H, form the secondary alcohol structure.Work as R, R ' and R and " when middle neither one is H, form tertiary alcohol structure.The tertiary alcohol than secondary alcohol more preferably.Diluent is preferably inert and be 5 or replaced by water easily still less the time when the total number of carbon atoms.

The example of useful secondary alcohol comprises the 2-butanols, and 2-propanol, menthol, Hexalin, cyclopentanol and exonorborn alcohol, 2-amylalcohol, 3-amylalcohol, 2-be alcohol, and 3-is alcohol, 3-methyl-2-butanols, 2-enanthol, sec-n-octyl alcohol, 2-nonyl alcohol, 2-decanol, 3-capryl alcohol, 2-Norborneol etc.

The example of the useful tertiary alcohol comprises the tert-butyl alcohol, tert-pentyl alcohol, 2-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 3-methyl-3-amylalcohol, 1 methyl cyclohexanol, 2-methyl-2-be alcohol, and 3,7-dimethyl-3-capryl alcohol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-enanthol, 2-methyl-sec-n-octyl alcohol, 2-methyl-2-nonyl alcohol, 2-methyl-2-decanol, 3-methyl-3-be alcohol, 3-methyl-3-enanthol, 4-methyl-4-enanthol, 3-methyl-3-capryl alcohol, 4-methyl-4-capryl alcohol, 3-methyl-3-nonyl alcohol, 4-methyl-4-nonyl alcohol, 3-methyl-3-capryl alcohol, 3-ethyl-3-be alcohol, 3-methyl-3-enanthol, 4-ethyl-4-enanthol, 4-propyl group-4-enanthol, 4 isopropyls-4-enanthol, 2,4-dimethyl-2-amylalcohol, 1-methylcyclopentanol, 1-ethyl cyclopentanol, 1-ethyl cyclopentanol, 3-hydroxy-3-methyl-1-butylene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxyl group-2-methyl-2-propanol, 2,3,4-trimethyl-3-amylalcohol, 3,7-dimethyl-3-capryl alcohol, 2-phenyl-2-butanols, 2-methyl isophthalic acid-phenyl-2-propanol and 3-ethyl-3-amylalcohol etc.

Can use single alcohol or two or more above listed alcohol or two or more mixture that meets the alcohol of said structure to prepare polymer of the present invention as diluent.

In certain embodiments, preferred pure diluent is the second month in a season and the tertiary alcohol that contains at least 4 carbon.Preferred pure diluent comprises the tert-butyl alcohol, tert-pentyl alcohol, 2-butanols, 2-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 3-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, 3,7-dimethyl-3-capryl alcohol.

Here, most preferred diluent is a hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol, the tert-butyl alcohol, 3-methyl-3-amylalcohol, isopropyl alcohol, tert-pentyl alcohol, ethyl lactate, methyl lactate, isopropyl lactate, 3,7-dimethyl-3-capryl alcohol, dimethyl formamide, dimethyl acetylamide, dimethyl propylene amide, N-Methyl pyrrolidone and its mixture.Can be used for the other diluent of the present invention referring to United States Patent (USP) 6,020,445, it is hereby incorporated by.

In one embodiment of the invention, diluent is water miscible under processing conditions, and is easy in a short time water and washes off from eyeglass.Suitable water-soluble diluent comprises 1-ethyoxyl-2-propanol, 1-methyl-2-propanol, tert-pentyl alcohol, tripropylene glycol methyl ether, isopropyl alcohol, 1-Methyl-2-Pyrrolidone, N, N-dimethyl propylene amide, ethyl lactate, dipropylene glycol methyl ether, its mixture etc.Use water miscible diluent to make the back molding process only to make water or comprise water and carry out as the aqueous solution of key component.

In one embodiment, the amount of diluent is usually less than about 50wt% of reactant mixture, preferably is lower than about 40wt%, more preferably between the about 30wt% of the about 10-of the gross weight of reaction mixture components.

Diluent also can comprise other component, such as releasing agent.Suitable releasing agent is water miscible and helps the eyeglass demoulding.

Polymerization initiator comprises such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azo isobutyronitrile etc. and generates the chemical compound of free radical and add the photoinitiator system of diketone, its mixture etc. such as aromatics alpha-alcohol ketone, alkoxyl oxygen Benzoinum, acetophenone, acylphosphine oxide and tertiary amine under suitably high temperature.The example of exemplary light trigger is the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; two (2; 6-dimethoxy benzoyl)-2,4,4-trimethylphenyl phosphine oxide (DMBAPO); two (2; 4, the 6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819), 2; 4; 6-trimethyl benzyl diphenyl phosphine oxide, 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide; the combination of benzoic acid methyl ester and camphorquinone and 4-(N, N--dimethylamino) ethyl benzoate.Commercially available visible light initiator system comprises Irgacure 819, and Irgacure 1700, and Irgacure 1800, Irgacure 1850 (deriving from Ciba SpecialtyChemicals company all) and Lucirin TPO initiator (deriving from BASF AG).Commercially available ultraviolet initiator comprises Darocur 1173 and Darocu 2959 (Ciba Specialty Chemicals company).The amount that initiator is used for reactant mixture is the amount of effective initiation reaction mixture light polymerization, for example per 100 parts of about 2 weight portions of the about 0.1-of activated monomer.According to the polymerization initiator that uses, the polymerization of reactant mixture can suitably select to use heating or visible light or ultraviolet light or other modes to cause.Perhaps, do not use under the situation of light trigger having, for example electron beam causes.But when using light trigger, preferred initiator is a 1-hydroxy-cyclohexyl benzophenone and two (2,6-dimethoxy benzoyl)-2,4, the combination of 4-trimethylphenyl phosphine oxide (DMBAPO), and preferred polymerization initiating method is that visible light causes.Two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides (Irgacure 819) most preferably.

All preferable range that contain silicone component (permeable component of oxygen and compatible components) are in the about 5-99wt% of the gross weight of reactive component, more preferably from about 15-90wt%, the most preferably from about about 80wt% of 25-.The preferable range of compatible components is the about 90wt% of about 5-, the about 80wt% of preferably about 10-, the most preferably from about about 50wt% of 20-.In reactant mixture, the preferable range of hydrophilic monomer is the about 80wt% of about 5-of reactive component, more preferably from about the about 60wt% of 5-, the most preferably from about about 50wt% of 10-.The preferable range of high molecular hydrophilic polymer is the about 15wt% of about 1-, more preferably from about the about 15wt% of 3-, the most preferably from about about 12wt% of 5-.The preferable range of macromonomer is the about 50wt% of about 5-, the about 50wt% of preferably about 10-, the more preferably from about about 45wt% of 15-.Above all scopes are all in the gross weight of all reactive components.

The preferable range of diluent is in the about 70wt% of the about 0-of the weight of all components in the complete reaction mixture, and more preferably from about the about 50wt% of 0-is more preferably the about 40wt% of about 0-, in certain embodiments, and the about 30wt% of 10-most preferably from about.The amount of required diluent is along with the character of reactive component and relative quantity and change.

The present invention also comprises, by or silicon hydrogel, bio-medical instrument, Ophthalmoligic instrument and the contact lens formed by prescription as follows basically:

The Wt% component
					CC	HMWHP	ASCM	SCM	HM
5-90	1-15,3-15 or 5-12	0	0	0
					10-80	1-15,3-15 or 5-12	0	0	0
15-55	1-15,3-15 or 5-12	0	0	0
					5-90	1-15,3-15 or 5-12		5-50
10-80	1-15,3-15 or 5-12		10-50
					15-55	1-15,3-15 or 5-12		15-45
5-90	1-15,3-15 or 5-12	0-80,5-60 or 10-40	5-50；10-50； 15-45	0-70,5-60 or 10-50
					10-80	1-15,3-15 or 5-12	0-80,5-80 or 10-40	5-50；10-50； 15-45	0-70,5-60 or 10-50
15-55	1-15,3-15 or 5-12	0-80,5-60 or 10-40	5-50；10-50； 15-45	0-70,5-80 or 10-50

CC is a compatible components

HMWHP is the high molecular hydrophilic polymer

ASCM is the other siloxanyl monomers that contains

HM is a hydrophilic monomer

SCM contains the macromonomer of siloxanes

Therefore, the present invention includes the silicon hydrogel, bio-medical instrument, Ophthalmoligic instrument and the contact lens that respectively have listed composition in the table, it has described 261 kinds of possible compositing ranges.Above-listed each scope all starts with " pact " word.The precondition that the combination of above-mentioned scope exists be listed component and arbitrarily other components add up to 100wt%.

In preferred embodiments, reactive component comprises the SiGMA of about 28wt%; The MW of about 31wt% is the end capped polydimethylsiloxane of the end capped single normal-butyl of the monomethacryloxypropterminated of 800-1000, " mPDMS ", the N,N-DMAA of about 24wt%, " DMA ", the methacrylic acid 2-hydroxyethyl ester of about 6wt%, " HEMA ", the tetraethylene glycol dimethacrylate of about 1.5wt%, " TEGDMA ", the polyvinylpyrrolidone of about 7wt%, " K-90PVP "; All the other comprise minor amounts of additives and light trigger.Polymerization most preferably at about 23% (in weight % of monomer and the combination of diluent blend) 3, is carried out under the existence of 7-dimethyl-3-capryl alcohol diluent.

In second preferred embodiment, reactive component comprises the SiGMA of about 30wt%, the mPDMS of about 23wt%, the DMA of about 31wt%, the ethylene glycol dimethacrylate of the about 1wt% of about 0.5-, " EGDMA ", the K-90PVP of about 6wt%; With the HEMA of about 7.5wt%, all the other comprise minor amounts of additives and light trigger.Polymerization most preferably at the tert-pentyl alcohol that accounts for the about 29wt% of reactant mixture as carrying out in the presence of the diluent.Diluent also can comprise about 11wt% low-molecular-weight PVP (it is about 5,000 that Mn is lower than, and preferably is lower than about 3,000).

In the 3rd preferred embodiment, reactive component comprises that the macromonomer of about 11-18wt% is (with 3-isopropenyl-α of 8wt%, the HEMA of about 24wt% of alpha, alpha-dimethyl benzyl isocyanate ester functional; The MMA of about 3wt%; The GTP product of methacryloxypropyl three (trimethylsiloxy) silane of about 33wt% and the end capped polydimethylsiloxane of the end capped monobutyl of monomethacryloxypropterminated of about 32wt%); The mPDMS of about 18-30wt%, the acPDMS of about 2-10wt%, the DMA of about 27-33wt%, the TRIS of about 13-15wt%, the K-90 PVP of the HEMA of about 2-5wt% and about 5-7wt%; All the other comprise minor amounts of additives and light trigger.Polymerization most preferably comprises 3 at about 25-30% (in the weight % of monomer and the combination of diluent blend), and the diluent of 7-dimethyl-3-capryl alcohol carries out under existing.

In the 4th preferred embodiment, reactive component comprises the macromonomer (perfluor ether and mean molecule quantity by the about 1030 gram/moles of mean molecule quantity are the α of about 2000 gram/moles, and ω-hydroxypropyl terminated polydimethylsiloxane, isophorone diisocyanate and methacrylic acid isocyanates ethyl ester forms) of the about 40wt% of about 15-; The SiGMA of about 40-about 52%, the methacrylate of 3-three (trimethylsiloxy) the silicyl propyl group of the about 5wt% of about 0-, " TRIS ", the DMA of the about 32wt% of about 22-, the K-90 PVP of the about 8wt% of about 3-, all the other comprise minor amounts of additives and light trigger.Polymerization is most preferably about 40% at about 15-, carries out under the diluent of preferably about 20-about 40% (in the weight % of monomer and the combination of diluent blend) exists, and in certain embodiments, described diluent preferably can be ethanol, 3,7-dimethyl-3-capryl alcohol.

Processing

Bio-medical instrument of the present invention prepares by the following method: promptly, with high molecular hydrophilic polymer, compatible components, add one or more following compositions: component, hydrophilic monomer, additive (" reactive component ") and the diluent (" reactant mixture ") that strengthens oxygen permeability mixes with initiator and solidify to form product by suitable condition, then can be by with methods such as machined into, cuttings described product being shaped to suitable shape.Perhaps, can place mould to reactant mixture, then be solidified into suitable goods.

All be known the curing of the whole bag of tricks reactant mixture in contact lens production, comprise rotated mold filing and static casting.The rotated mold filing method is referring to United States Patent (USP) 3,408, and 429 and 3,660,545, static casting method is referring to United States Patent (USP) 4,113, and 224 and 4,197,266.The method for optimizing that preparation comprises the contact lens of polymer of the present invention is by silicon hydrogel is directly molded, this method economy, and can the accurate net shape of controlling the aquation eyeglass.For this method, reactant mixture is placed final silicon hydrogel with hope, be in the mould of water-swellable polymer shape, and make reactant mixture be subjected to the condition that can make monomer polymerization, thereby make the polymer/diluent mixture of the shape of product that is final hope.Then, with solvent to this polymer/diluent mixture handle with remove diluent and final water consumption substitution it, obtain having the silicon hydrogel of final size and shape, the size and dimension of the polymer of its size and dimension and original molded/diluent goods is quite similar.This method can be used for making contact lens, further describes referring to United States Patent (USP) 4,495,313; 4,680,336; 4,889,664; With 5,039,459, it is hereby incorporated by.

Solidify

Another feature of the present invention is that a kind of curing silicone hydrogel formulation that is used for is to provide the method for enhanced wettability.Have now found that the gelling time of silicon hydrogel can be used for wettable Ophthalmoligic instrument is being provided, particularly select condition of cure during contact lens.Gelling time is the formation crosslinking polymer network, causes the viscosity of solidified reactant mixture to approach infinity and make reactant mixture become the aneroid time.Gel point is present under the concrete conversion ratio, and is irrelevant with reaction condition, therefore can be as the sign of reaction rate.Have now found that for given reactant mixture, gelling time can be used for determining to give the condition of cure of desirable wettability.Therefore, in the method for the invention, reactant mixture is in certain gelling time point or above curing, this gelling time makes resulting device have improved wettability when using under not carrying out hydrophilic coating or surface-treated situation, perhaps more preferably sufficient wettability (" minimum gelling time ").Preferably, improved wettability is meant with the prescription that does not have high molecular polymer and compares that the dynamic contact angle that advances reduces at least 10%.Preferably long gelling time is because they can provide the processing elasticity of improved wettability and increase.

For different silicon hydrogel prescriptions, gelling time will change.Condition of cure also influences gelling time.For example, the concentration of cross-linking agent will impact gelling time, increases crosslinker concentration and can reduce gelling time.Increase radiant intensity (for photopolymerization) or temperature (for thermal polymerization), efficiency of initiation (perhaps by selecting more effective initiator or irradiation bomb, perhaps the initiator of absorbed radiation more effectively in selected irradiation range) and also will reduce gelling time.Temperature and diluent type and concentration also can influence gelling time in the intelligible mode of those skilled in the art.

Minimum gelling time can be by selecting given prescription, change a factor in the middle of the above-mentioned factor and measure gelling time and contact angle being determined.Minimum gelling time is meant and is higher than the gained eyeglass by the point of the time point of general moistening.Below minimum gelling time, eyeglass is generally not wettable.For " generally wettable " contact lens, be meant that the dynamic contact angle that advances is lower than about 70 degree, preferably be lower than the eyeglasses of about 60 degree, perhaps tear film splitting time equals or exceeds ACUVUE^The contact lens of eyeglass.Therefore, it will be understood to those of skill in the art that the statistics factor of considering that test changes, may be a scope at the minimum gel point of this definition.

In certain embodiments, minimum gelling time was at least about 30 seconds when using radiation of visible light, was preferably greater than about 35 seconds, had been considered to favourable more preferably greater than about 40 seconds.

Curing can be used heating, ionization or actinic radiation, for example electron beam, X ray, ultraviolet or visible light, and promptly wave-length coverage is carried out for the electromagnetic radiation or the corpuscular radiation of about 800 nanometers of about 150-.Preferred radiation source comprises that wavelength is the ultraviolet or the visible light of about 700 nanometers of about 250-.Suitable radiation source comprises uviol lamp, fluorescent lamp, electric filament lamp, mercury lamp and daylight.Comprise that in reactant mixture ultraviolet absorption compound (for example, as ultraviolet blocking-up or light-sensitive material in) the embodiment, solidifies and carries out (such as being undertaken by visible light or heating) by the mode that is different from ultraviolet radiation.In preferred embodiments, radiation source is selected from UVA (about 400 nanometers of about 315-), UVB (about 315 nanometers of about 280-) or visible light (about 450 nanometers of about 400-).In a further preferred embodiment, reactant mixture comprises ultraviolet absorption compound, and it uses visible-light curing.In many embodiments, under low-intensity, solidify so that the gelling time of wishing minimum will be useful.Term used herein " low-intensity " meaning refers to that intensity is at about 0.1mW/cm²-Yue 6mW/cm²Between, preferably at about 1mW/cm²-3mW/cm²Between.Hardening time is long, is generally approximately more than 1 minute, and about 60 minutes of preferably about 1-was more preferably about 1-about 30 minutes.This low-intensity curing slowly provides the minimum gelling time of hope and a kind of method that preparation demonstrates the Ophthalmoligic instrument of good wettability.

Initiator concentration also influences gelling time.Therefore, in certain embodiments, preferably have low relatively light-initiated dosage, be generally 1% or still less, preferred 0.5% or still less.

Temperature no less important during reaction mixture cured.When temperature is increased to when being higher than ambient temperature, the optical haze degree of resulting polymers reduces.The temperature that effectively reduces the optical haze degree comprises the optical haze degree that makes the gained eyeglass and compare reduction at least about 20% temperature with the eyeglass of same combination preparation under 25 ℃.Therefore, suitable solidification temperature comprises that greater than about 25 ℃ temperature preferred temperature is about 25 ℃-70 ℃, more preferably from about 40 ℃-70 ℃.The accurate setting of condition of cure (temperature, intensity and time) will depend on selected lens materials component and, according to instruction of the present invention, within those of ordinary skills' cognitive range.Curing can be carried out in one or more curing area.

Condition of cure must be enough to form polymer network by reactant mixture.The resulting polymers network is by the diluent swelling and have the die cavity form.

The demoulding

After eyeglass solidifies, must from mould, remove them.Unfortunately, the silicone component that is used for the eyeglass prescription makes the finished product eyeglass send out " gluing " and be difficult to discharge from lens mold.Can use solvent, make the eyeglass demoulding (from moving tool up away of half or bearing lens of mould) such as organic solvent.Yet, in one embodiment of the invention, at least a low-molecular-weight hydrophilic polymer joins in the reactant mixture, and reactant mixture is shaped to the goods of hope, solidify and in water or contain, basically by with the aqueous solution of forming by low quantity of surfactant in the demoulding.The low-molecular-weight hydrophilic polymer can be any polymer that has as the structure that high molecular polymer is defined, but its molecular weight will make that the low-molecular-weight hydrophilic polymer leaches or elimination discharges from mould to help eyeglass from eyeglass under demoulding condition.Suitable molecular weight comprises and is lower than about 40,000 dalton, preferably is lower than about 20,000 dalton.It will be understood by those skilled in the art that above-mentioned molecular weight is a mean molecule quantity, and as long as mean molecule quantity within described scope, have the molecular weight of a certain amount of material be higher than may also be suitable during given mean molecule quantity.Preferably, low-molecular weight polymer is selected from water soluble polyamide, lactams and Polyethylene Glycol, and composition thereof, more preferably polyvinyl pyrrolidone, Polyethylene Glycol, poly--2-ethyl-2- azoles quinoline (derives from Plymer Chemistry Innovations, Tuscon, AZ), polymethylacrylic acid, poly-(L-lactic acid), polycaprolactam, polycaprolactone, pcl-diol acid lactone, polyvinyl alcohol, polyhema, polyacrylic acid, poly-(1-glycerol methacrylate), poly-(2-ethyl-2- azoles quinoline), poly-(methacrylic acid 2-hydroxypropyl ester), poly-(2-vinylpyridine-N-oxide), polyacrylamide, PMAm etc.

The consumption of low-molecular-weight hydrophilic polymer can account for the about at most 20wt% of reactive component, the preferred about 20wt% of about 5-that amounts to.

Suitable surfactant comprises nonionic surfactant, comprises betanin, amine oxide, its combination etc.The example of suitable surfactant comprises TWEEN  (ICI), DOE120 (Amerchol/Union Carbide) etc.The consumption of surfactant can be about at most 10,000ppm, the about 1500ppm of preferably about 250ppm-, the more preferably from about about 1200ppm of 100ppm-.

Suitable releasing agent is the low-molecular-weight releasing agent, it comprises 1-methyl-4-piperidones, 3-morpholino-1,2-propylene glycol, tetrahydrochysene-2H-pyrans-4-alcohol, glycerin methylal, ethyl-4-oxo-1-piperidine carboxylic acid ester, 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidone and 1-(2-ethoxy)-2-Pyrrolidone.

Under the situation that does not have the low-molecular-weight hydrophilic polymer, can the demoulding in containing the aqueous solution of at least a organic solvent by the eyeglass that reactant mixture is made.Suitable organic solvent is a hydrophobicity, but can be miscible with water.Suitable have alcohol, an ether etc., and more particularly primary alconol, particularly isopropyl alcohol, DPMA, TPM, DPM, methanol, ethanol, propanol and composition thereof are suitable examples.

Suitable calcining temperature scope is about ambient temperature-Yue 100 ℃, and preferred about 70 ℃-95 ℃, temperature is high more, and the demould time that provides is fast more.Stir,, also can be used for reducing demould time such as ultrasonication.Other modes as known in the art also can be used for removing eyeglass from mould such as vacuum noz(zle).

Diluent displacement/aquation

Usually, after reaction mixture cured, resulting polymers will with solvent processing with remove diluent (if you are using), unreacted component, by-product etc. and with polymer hydration to form hydrogel.Perhaps, dissolubility feature according to the hydrogel component, originally the solvent of Shi Yonging can be an organic liquid, such as ethanol, methanol, isopropyl alcohol, TPM, DPM, PEG, PPG, glycerol, its mixture, perhaps the mixture of one or more this organic liquids and water is used pure water (perhaps normal saline) extraction subsequently.Organic liquid also can use with the form of " presoak ".Behind the molding, eyeglass can soak (time is up to about 30 minutes, about 30 minutes of preferably about 5-) tout court in the mixture of organic liquid or organic liquid and water.After the pre-soaking, eyeglass is use extractant aquation further.

In certain embodiments, it mainly is water that preferable methods is used, and the preferred water yield is greater than 90%, and more preferably the water yield is greater than 97% extractant.Other component can comprise the salt such as sodium chloride, sodium tetraborate, boric acid, DPM, TPM, ethanol or isopropyl alcohol.Eyeglass generally is discharged into from mould in this extractant, and is optional with the mode that stirs or make extractant continuous-flow above eyeglass.This method can be carried out under preferred 20-98 ℃ the temperature at 2-121 ℃.This method can be carried out under high pressure (particularly when temperature surpasses 100 ℃), but more generally carries out under ambient pressure.Can be in a kind of solution (solution that for example contains some demolding aids) with the eyeglass demoulding, and then it is transferred in the another kind of solution (for example final packing liquid), although also can be in the solution identical with their solution of packing with the eyeglass demoulding.With this extractant eyeglass is handled and to be carried out about 30 seconds-Yue 3 days time, about 30 minutes of preferably about 5-.Selected aquation solution can comprise minor amounts of additives in addition, such as surfactant and/or demolding aids.Suitable surfactant comprises nonionic surfactant, such as betanin and amine oxide.Concrete surfactant comprises TWEEN 80 (deriving from Amerchol), DOE 120 (deriving from Union Carbide), Pluronics, methylcellulose, its mixture etc., and its addition can be in the about 0.01wt%-of the gross weight of used aquation solution about 5%.

In one embodiment, eyeglass can be used " descending " method aquation, and wherein solvent is progressively replaced in hydration process.Suitable descending method has at least two, and at least three, at least four steps, wherein a part of water replacement of solvent in certain embodiments.

After the polymer hydration, silicon hydrogel preferably includes the water in the about 60wt% of the about 10-of the gross weight of silicon hydrogel, more preferably from about the water of the about 55wt% of 20-, the most preferably from about water of the about 50wt% of 25-.The more detailed data of silicon hydrogel contact lens preparation method is referring to United States Patent (USP) 4,495,313; 4,680,336; 4,889,664; With 5,039,459, it is hereby incorporated by.

The solidified bio-medical instrument of the present invention also can demonstrate good resistance tocrocking in vivo even without coating.When bio-medical instrument is Ophthalmoligic instrument, can by mensuration wear with during the sedimental amount of upper lens surface measure its anti-biodeterioration, this surface deposits often is called as " lipid deposition thing ".

The lens surface deposit is measured as described below: eyeglass is placed on the human eye, wears with 30 minutes and 1 all evaluation with corneal microscope afterwards.In evaluation procedure, for the chip that deposit and the back side are caught makes a distinction, patient be required to blink several times and manual " promotion " eyeglass.Because be dispersive (promptly gluey projection) or film like, so the deposit at the front and the back side is come by classification.The surface deposits of front provides strong reflection, and the surface deposits at the back side then can not.The chip that catch at the deposit and the back side nictation or on push away in the test by difference and come.Deposit will be moved, and the chip that catch at the back side will be still motionless.According to the percentage ratio of examined eyeglass, deposit is divided into 5 types: do not have (＜about 1%) slight (about 1-about 5%), gentle (about 6%-about 15%), moderate (about 16%-about 25%), serious (greater than about 25%).10% difference is considered to significant clinically between all types of.

Ophthalmoligic instrument of the present invention also demonstrates low optical haze degree, excellent wetting capacity and modulus.

The optical haze degree is to be put in the normal saline in the transparent pond that is in black background top by testing eyeglass, shine from bottom to top with the angle of spending perpendicular to eyeglass pond direction 66 with the optical fiber lamp, and with camera from capturing the image of eyeglass.By in 10 millimeters in eyeglass central authorities, carrying out integration, be-1.00 CSI Thin Lens  to the scattered light image of quantitative analysis subtracting background recently with diopter then, at random diopter is set at 100 for the light haze value of-1.00 CSI Thin Lens , the light haze value when not having eyeglass is set at 0.

Wettability is by measuring with Wilhelmy balance mensuration contact angle or DCA (using BBS usually) down at 23 ℃.Wetting power between lens surface and the BBS is that standby Wilhelmy microbalance is measured when sample is being dipped into or is pulling out from normal saline.Use following formula:

F=2 γ pcos θ or θ=cos^-1(F/2 γ p) wherein F is wetting power, and γ is the surface tension of test fluid, and p is the girth of sample on meniscus lens, and θ is a contact angle.Usually, from dynamic moistening test, obtain two contact angle-advancing contact angles and receding contact angle.Advancing contact angle is that the moistening test portion when sample is being dipped into the test fluid obtains.Each composition is measured 4 eyeglasses at least and records of values is got off.

But DCA is good prophesy means of wettability on the eyes always not.Preceding eyeglass tear film non-intruding break-up time (PLTF-NIBUT) is the assay method of " clinical " eyeglass wettability in a kind of body.Use corneal microscope when measuring PLTF-NIBUT and be used for the annulus fluorescent tear display (Keeler Tearscope Plus) that Noninvasive is observed the tear film.Eyes after nictation open and tear film in the contact lens front in occur experiencing between first skin dark stain time sheet be PLTF-NIBUT.Eyeglass is placed on the eyes back 30 minutes with 1 week after measure PLTF-NIBUT.Carrying out three on each interval measures and reading of average one-tenth.Measuring PLTF-NIBUT on two eyes, from right eye, is left eye then.

With " on push away " test determination mobility.Patient's eye is on the primary of gaze position.On push away test and be meant from the eyelid of bottom and upwards promote eyeglass gently with pointing.Estimate resistance that eyeglass moves upward and according to following yardstick classification: 1 (over-drastic unacceptable moving), 2 (moderate, but acceptable moving), 3 (best moves), 4 (minimum, but acceptable moving), 5 (inadequate unacceptable moving).

Eyeglass of the present invention demonstrates the modulus at least about 30psi, the about 90psi of preferably about 30-, the more preferably from about about 70psi of 40-.Modulus is to measure with the crosshead constant speed mobile model tensile testing machine that the load cell that drops to initial metering height is housed.Suitable testing machine comprises that model is 1122 Instron.Long 0.522 inch, " ear " wide 0.276 inch and " neck " wide 0.213 inch Os Canitis shape sample installs on the grip handle and with the constant speed tension force of 2 inch per minute clocks it elongated up to fracture.Length (Lf) when measuring length (Lo) that working sample is initial and sample breakage.12 samples of each composition measuring, the record meansigma methods.Modulus in tension is measured on the initial straight line segment of tension force/strain curve.

By the contact lens of the present invention's preparation, by the O of polarography determination₂The Dk value is the about 300barrer of about 40-.Eyeglass is placed on the pick off, uses the aperture plate carrier cover then in the above.Eyeglass is exposed to humidification 2.1%O₂Atmosphere in.Using by diameter is that the polarography oxygen sensor that 4 millimeters au cathode and silver ring anode are formed is measured the oxygen that spreads by eyeglass.Those values that reference value is to use this method to measure on commercially available contact lens.By deriving from Bausch ﹠amp; The value that the Balafilcon A eyeglass of Lomb obtains is about 79barrer.The value that obtains from the Etafilcon eyeglass is 20-25barrer.1barrer=10^-10(cm³Gas * cm²)/(cm³Polymer * s * cmHg).

Gelling time is measured in order to following method.With the viscometer monitoring photopolymerization reaction of the ATSStress Tech that the photocuring auxiliary facilities is housed, described photocuring auxiliary facilities is made up of with the radiation feed system that band pass filter is housed the cell of quartzy lower shoe of having of temperature control and aluminum upper plate.Produce radiation being equipped with on the Novacure mercury-arc lamp of iris and computer-controlled optical gate, this radiation is transported on the piezoid of viscometer by liquid light guide.Filter is the band pass filter of 420 nanometers (20nm FWHM), and it is simulated by the light that sends from the TL03 bulb.The transmitted intensity by the IL1400A radiometer measurement on the surface of quartz window is controlled at ± 0.02mW/cm by iris²Temperature is controlled at 45 ± 0.1 ℃.After on the lower shoe that about 1 milliliter degassing reactant mixture is placed viscometer, be that 25 millimeters upper plate is reduced to and is higher than 0.500 ± 0.001 millimeter place of lower shoe, make this state keep reaching gel point up to reaction with diameter.Make sample reach thermal balance (about 4 minutes, align measure by the shear viscosity that continues), open the lamp box dark slide afterwards and begin reaction.During this time, when sample reaches thermal balance, combustor is purged with the speed of nitrogen with 400sccm.In course of reaction, the tension force that is produced by the dynamic stress (fast vibration mode) that is suitable for continuously monitored in viscometer, and the time period that wherein is lower than complete alternation is used for calculating the pulling force under the controlled stress that is suitable for.COMPUTER CALCULATION goes out dynamic shear modulus (G), loss modulus (G "), and viscosity (v^*) with exposure time change.When reaction was carried out, modulus of shearing was increased to＞0.1MPa from＜1Pa, and (=G "/G ') is reduced to by infinity nearly and is lower than 1 tan δ.For the measurement of carrying out among the present invention, gelling time is the time that tan δ equaled 1 o'clock.(as G '=G " time cross point).When G ' reaches 100Pa (after gel point soon), remove restriction, in solidification process so that the slit between the upper and lower bottom plate can change along with the contraction of reactive monomer mix to upper plate.

Should be appreciated that above-mentioned all tests all have a certain amount of intrinsic test error.Therefore, all should be in the result of this record as absolute figure, but based on the numerical range of the degree of accuracy of concrete test.

In order to demonstrate the invention, comprise following examples.These embodiment are not construed as limiting the present invention.They only mean a kind of enforcement method of the present invention that proposes.Knowledgeable people in contact lens and other professional fields can find and implement additive method of the present invention.But those methods are deemed to be within the scope of the present invention.

Embodiment

Abbreviation below in following examples, using:

The acrylic acid 2-methyl of SiGMA 2--2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-(trimethyl silyl) oxygen] the disiloxane base] propoxyl group] propyl ester

The DMA N,N-DMAA

HEMA methacrylic acid 2-hydroxyl ethyl ester

MPDMS MW (Mn) is the end capped polydimethylsiloxane of the end capped single normal-butyl of the monomethacryloxypropterminated of 800-1000

Norbloc 2-(2 '-hydroxy-5-methyl base acrylyl oxy-ethyl phenyl)-the 2H-benzotriazole

CGI1850 1-hydroxy-cyclohexyl benzophenone and two (2,6-dimethoxy benzoyl)-2,4,1: 1 (weight) blend of 4-trimethylphenyl phosphine oxide

PVP gathers (N-vinyl pyrrolidone) (K value=90)

The product of Blue HEMA reactive blue 4 and HEMA, as United States Patent (USP) 5,944,853 embodiment 4 is described

The IPA isopropyl alcohol

D3O 3,7-dimethyl-3-capryl alcohol

MPDMS-OH list-(3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group is end capped, the end capped polydimethylsiloxane of monobutyl (molecular weight is 1100)

The TEGDMA tetraethylene glycol dimethacrylate

The TrEGDMA triethylene glycol dimethacrylate

TRIS 3-methacryloxypropyl three (trimethylsiloxy) silane

MPD 3-methacryloxypropyl (pentamethyl disiloxane)

Two (trimethylsiloxy) methyl-monosilanes of MBM 3-methacryloxypropyl

AcPDMS pair-3-methacryloxypropyl-2-propoxyl propyl group polydimethylsiloxane

TRIS-HEMA methacrylic acid 2-trimethylsiloxy ethyl ester

The MMA methyl methacrylate

The THF oxolane

TBACB 3-chlorobenzoic acid tetrabutylammonium

TMI 3-isopropenyl-α, the α-Er Jiajibianji isocyanates

The IPL isopropyl lactate

CGI819 2,4,6-trimethyl benzyl diphenyl phosphine oxide

In whole embodiment, all use IL 1400A radiometer, with XRL 140A sensor determination intensity.

Embodiment 1-10

The listed reactive component of table 1 and diluent (D3O) mixed together under 23 ℃ or roll all dissolved up to all components at least about 3 hours.Reactive component is recorded as the percetage by weight of all reactive components, and diluent is recorded as the reactant mixture percetage by weight.Reactant mixture is placed thermoplasticity contact lens mould (the copolymer Topas  by ethylene that derives from Ticona Polymers company and norborene makes) and uses Philips TL 20W/03T fluorescent light bulb at N₂In, shone about 20 minutes down at 45 ℃.Open mould, and eyeglass is extracted the IPA/H of 50: 50 (wt)₂In the O solution, and at room temperature in IPA, soak about 15 hours, placed deionized water about 30 minutes to remove remaining diluent and monomer, then in BBS balance at least about 24 hours, and 122 ℃ of following heat treatments 30 minutes.The performance of gained eyeglass is shown in table 1.

Table 1

Embodiment	1	2	3	4	5	6	7	8	9	10
											Comp
SiGMA	28	30	28.6	28	31	32	29	39.4	20	68
											PVP(K90)	7	10	7.1	7	7	7	6	6.7	3	7
DMA	23.5	17	24.5	23.5	20	20	24	18.4	37	22
											MPDMS	31	32	0	31	31	34	31	29.8	15	0
TRIS	0	0	0	0	0	0	0	0	15	0
											HEMA	6	8	6.1	6	6.5	3	5.5	2.9	8	0
Norbloc	2	2	0	2.0	2	2	2	1.9	0	0
											CGI 1850	0.98	1	1.02	1	1	1	1	1	1	0
TEGDMA	1.5	2	1.02	1.5	1.5	1	1.5	1.9	0	2
											TrEGDMA	0	0	0	0	0	0	0	0	1	0
Blue HEMA	0.02	0	0	0	0	0	0	0	0	0
											mPDMS-OH	0	0	31.8	0	0	0	0	0	0	0
Darocur 1173	0	0	0	0	0	0	0	0	0	1
D30％	23	26	17	23	23	29	32	28	17	27
Performance
											％EWC1	36	33	39	40	36	37	39	25	48	29
Modulus (psi)	68	78	112	81	67	50	66	92	43	173
											The % percentage elongation	301	250	147	294	281	308	245	258	364	283
DCA2(advancing)	62	55	58	64	72	65	61	55	92	72
											Dk3(marginal correction)	103	111	101	131	110	132	106	140	64	76

1. equilibrium moisture content

2. dynamic contact angle is measured by physiology borate-buffer saline with the Wilhelmy balance.

3. oxygen permeability has passed through the edge calibration, and unit is Barrer.

The result of embodiment 1-10 shows that reaction mixture components and their amount can be carried out substantial variation, meanwhile still can provide to have good mechanical performance and the equilibrated uncoated eyeglass of wettability.The contact angle of embodiment 9 (DCA) may be too high, be difficult to form can clinical moistening eyeglass, and its modulus may be than low at the required modulus of the eyeglass of mechanical properties practicality.The SiGMA concentration that embodiment 9 comprises minimum (20%).Because SiGMA reduces, therefore, can in prescription, add less PVP and compatible reactant mixture still is provided.Therefore, these embodiment show, SiGMA is effectively in compatible PVP, and when having sufficient SiGMA and PVP, just can produce the wettability with hope and the eyeglass of other mechanical performances under the situation of not carrying out any form surface modification.

Embodiment 11

Under the situation of not controlling solidification intensity, make eyeglass again with embodiment 1 prescription.Its mechanical performance is shown in the following table 2.Use ACUVUE  2 eyeglasses thing in contrast, these eyeglasses are carried out clinical evaluation.Eyes are worn the test eyeglass, and the another eyes are worn ACUVUE  2 eyeglasses.Described eyeglass has 6 patients to wear usefulness, wears (excision in evening) daytime, and the persistent period was 1 week.During 1 week, its PLTF-NIBUT is 3.6 (± 3.0) seconds, by contrast, concerning ACUVUE goes up  2 eyeglasses, is 5.8 (± 2.5) seconds.To the test eyeglass, the surface deposits classification of front do not have to slight one-level have 50%, and concerning control lenses, have 100%.To test and control lenses, both mobilitys all are acceptable.

Embodiment 12

Except solidification intensity is reduced to 1.0mW/cm²Outside, repeat embodiment 11.Its mechanical performance is recorded in the following table 2.Use ACUVUE  2 eyeglasses thing in contrast, these eyeglasses are carried out clinical evaluation.The test eyeglass is worn in the one eye by 15 patients, wears (excision in evening) daytime, and the persistent period was 1 week, and ACUVUE  2 eyeglasses are worn in the another eyes.During 1 week, its PLTF-NIBUT is 8.2 (± 1.7) seconds, by contrast, concerning ACUVUE  2 eyeglasses, is 6.9 (± 1.5) seconds.To test and control lenses, all patients are not all having the surface deposits classification of front to slight one-level.To test and control lenses, both mobilitys all are acceptable.

Table 2

Embodiment	1	11	12
				％EWC	38	38	38
Modulus (psi)	68	74	87
				Percentage elongation	301	315	223
DCA	62	77	56
				Dk	103	127	102

Usually, embodiment 1,11 is consistent with mechanical performance result for the test of many times of same material of 12.But the clinical effectiveness of embodiment 11 (not controlling solidification intensity) and 12 (low controlled solidification intensity) is tangible different.For embodiment 11, wear with the wettability on the eyes (measuring) after 1 week than ACUVUE  2 eyeglasses poorer (3.6 pairs 5.8), and the eyeglass of half has slight above surface deposition by PLTF-NIBUT.The eyeglass of embodiment 12 (controlled low-intensity is solidified), the wettability on its eyes has demonstrated significant improvement, than ACUVUE  2 eyeglass appropriateness good (8.2 pairs 6.9), and does not have surface deposition.Therefore, use the low uncoated eyeglass that controlled curing provided hydrogel lenses with conventional aspect the eyes wettability the same good, sometimes also can be better.

Embodiment 13-17

With describe in the table 3 and comprise reactant mixture low or that do not comprise compatible components (being SiGMA in these embodiments) at room temperature constant speed mixed 16 hours.Even after 16 hours, it is muddy that each reactant mixture still keeps, and has some also to comprise precipitation.Therefore, these reactant mixtures can not be used to make eyeglass.

Table 3

Embodiment	13	14	15	16	17
						Form
SiGMA	0	0	0	10	20
						PVP(K90)	12	12	10	8.0	8.0
DMA	10	10	8.3	19	19
						MPDMS	37	37	30.8	35	28
TRIS	14	14	11.7	17	14
						HEMA	25	25	37.5	8.0	8.0
Norbloc	0	0	0	0	0
						CGI 1850	0	0	0	0	0
TEGDMA	1.0	1.0	0.83	2.0	2.0
						TrEGDMA	0	0	0	0	0
Blue HEMA	0	0	0	0	0
						mPDMS-OH	0	0	0	0	0
Darocur 1173	1.0	1.0	0.83	1.0	1.0
D30％	23	31	31	27	27

Embodiment 13-15 shows that the reactant mixture that does not contain any compatible components (SiGMA or mPDMS-OH) is inconsistent, and is not suitable for making contact lens.Embodiment 16 and 17 shows, when the concentration of compatible components is lower than about 20wt%, is not enough to compatible with a large amount of high molecular PVP.But, can find with embodiment 9 by comparing embodiment 17, less high molecular PVP (3wt%) can be comprised, and still compatible reactant mixture can be formed.

Embodiment 18-26

With 1.00 gram D30, the solution of 1.00 gram mPDMS and 1.00 gram TRIS places arrow-necked bottle (embodiment 18).Under about 20-23 ℃, in the quick blended under agitation thing, drip the solution of 12 parts of (weight) PVP (K90) and 60 parts of DMA, after solution is stirring 3 minutes, still keep muddy with magnetic stirring bar.Determine the amount of the DMA/PVP blend of adding, with the gram expression, record is as " mhc monomer sex index ".Use SiGMA (embodiment 19), MBM (embodiment 20), MPD (embodiment 21), acPDMS (n=10 wherein, embodiment 22), acPDMS (wherein n=20, embodiment 23), ISIGMA-3Me (embodiment 24) and TRIS2-HOEOP2 (embodiment 25) replace TRIS to repeat above-mentioned test as test silicone monomer.

Table 4

Embodiment	Siliceous one monomers	Mhc monomer sex index	SI∶OH
				18	SiGMA	1.8	3∶1
19	TRIS	0.07	4∶0
				20	MBM	0.09	3∶0
21	MPD	0.05	2∶0
				22	acPDMS(n＝10)*	1.9	11∶2
23	acPDMS(n＝20)*	1	21∶2
				24	iSiMAA-3Me	0.15	4∶0
25	TRIS2-HOEOP2	0.11	3∶2
				26	MPDMS-OH	0.64	～11∶2

AcPDMS, the structure of iSiGMA-3Me and TRIS2-HOEOP2 is as follows:

AcPDMS (n average out to 10 or 20):

The result shows shown in the table 4, compared with alternative siliceous one monomers, SiGMA, acPDMS (wherein n=10 and 20) and mPDMS-OH be easier to be introduced in the blend of diluent, another kind of siliceous one monomers, hydrophilic monomer and high molecular polymer (PVP).Therefore, compatibility index can be used for making the high molecular hydrophilic polymer such as PVP compatible greater than about 0.5 compatible siliceous one monomers.

Embodiment 27-35

Use the reactant mixture prescription of embodiment 1 to make eyeglass.With plastics contact lens mould (making) by the copolymer Topas  of ethylene that derives from Ticona Polymers company and norborene at nitrogen (＜0.5% O₂) middle store overnight, re-use afterwards.All be metered to the reactant mixture of 75 microlitres in each mould.Time shown in closed mould and the use table 5 and solidification intensity come the photocuring eyeglass.By using visible fluorescence bulb irradiation monomer mixture, under 45 ℃, solidify to form eyeglass.Use variable balast or light-filter to change light intensity, change and be divided into for two steps, be i.e. change intensity and changing hardening time.The selection of step 2 time will make identical (the about 830mJ/cm of total radiation energy for each sample²).

Isopropyl alcohol/deionized water mixture of using 60: 40 is with the demoulding of finished product eyeglass.Eyeglass is transferred in the container that contains 300g100% isopropyl alcohol (IPA).IPA of displacement in per 2 hours, 10 hours altogether.When finishing in about 10 hours, there is 50% IPA to remove and be replaced into deionized water, this container was rolled 20 minutes.After 20 minutes, the IPA with 50% removes and is replaced into deionized water, this container is rolled 20 minutes again.Eyeglass is transferred in the filling solution, rolled 20 minutes, test afterwards.

Table 5

Embodiment	Step 1 intensity (mW/cm2)	Step 1 time (min:sec)	Step 2 intensity (mW/cm2)	Step 2 time (min:sec)	Advancing contact angle
						27	1.1	8:55	5.5	1:28	51±1
28	1.1	2:48	5.5	2:21	55±2
						29	1.1	11:03	5.5	0:35	55±1
30	1.7	8:30	5.5	0:35	50±1
						31	1.7	1:37	5.5	2:21	55±1
32	1.7	4:04	5.5	1:28	54±2
						33	2.4	2:52	5.5	1:28	62±6
34	2.4	4:38	5.5	0:35	76±9
						35	2.4	1:09	5.5	0:35	78±6

The contact angle of embodiment 27-32 does not have significant difference, this show no matter hardening time of step 1 how, step 1 is lower than about 2mW/cm²Solidification intensity all can provide improved wettability for this eyeglass prescription.But will make whole cure cycle shorten the hardening time that it will be understood by those skilled in the art that step 1 short (such as embodiment 28 and 31 hardening times of using).In addition, be higher than embodiment 27-32 although should be noted that the contact angle appropriateness of embodiment 33-35, the eyeglass of embodiment 33-35 still can provide the wettability on the eyes of hope.

Embodiment 36-41

The method of using embodiment 1 with the reactive component of embodiment 1 with 25% or 40% D30 blend as diluent; the gained reactant mixture joins in the plastics contact lens mould (being made by ethylene that derives from Ticona Polymers company and norbornene copolymer Topas ) and in nitrogen atmosphere, at about 2.5mW/cm²Intensity under, in glove box, solidified 30 minutes, solidification temperature is shown in following table 6.As described in embodiment 1, with eyeglass from mould, remove, aquation and hot-pressing processing, measure the light haze value of eyeglass after the aquation.The results are shown in table 6, this result shows that under higher temperature, the light haze value reduces.The result shows that also the concentration of diluent reduces, and the optical haze degree also reduces.

Table 6

Embodiment	％D30	Temperature (℃)	The % mist degree	DCA(°)
					36	25	25	30(6)	99
37	25	50-55	12(2)	100
					38	25	60-65	14(0.2)	59
39	40	25	50(10)	68
					40	40	50-55	40(9)	72
41	40	60-65	32(1)	66

Optical haze degree (std.dev.)

The result of table 6 shows that the optical haze degree may reduce about 20% (41 couples of embodiment 39 of embodiment), and by improving solidification temperature, this reduction almost can about at most 65% (37 couples of embodiment 36 of embodiment).Diluent concentration is reduced to 25% by 40%, and the optical haze degree reduces about 40%-75%.

Embodiment 42-47

Use the method for embodiment 1 to make eyeglass by the prescription shown in the table 7, solidification temperature is 25 ℃, the about 2.5mW/cm of intensity², be 30 minutes hardening time.Mensuration optical haze degree percent also is recorded in the table 7.

Table 7

Embodiment	42	43	44	45	46	47
							SiGMA	28.0	28.0	28.0	28.0	28.0	28.0
mPDMS	31.0	31.0	28.0	28.0	28.0	28.0
							acPDMS (n＝10)	0.0	0.0	4.0	4.0	4.0	4.0
DMA	23.5	23.5	23.5	23.5	24.0	24.0
							HEMA	6.0	6.0	5.0	5.0	6.0	6.0
TEGDMA	1.5	1.5	1.5	1.5	0.0	0.0
							Norbloc	2.0	2.0	2.0	2.0	2.0	2.0
PVP(K- 90)	7.0	7.0	7.0	7.0	7.0	7.0
							CGI 1850	1.0	1.0	1.0	1.0	1.0	1.0
							D30	25.0	40	25.0	40.0	25.0	40.0
Performance
							Mist degree	30	50	7.3	14	26	25
Modulus (psi)	74	56	148	104	74	NT
							Percentage elongation (%)	326	395	188	251	312	NT
EWC(％)	38	41	33	35	38	39

The prescription (embodiment 42 and 46 and embodiment 43 and 47) that relatively contains same amount diluent and TEGDMA or acPDMS, the result shows, acPDMS is a kind of effective cross-linking agent, and it can compare the performance of eyeglass with those eyeglasses that TEGDMA are used as cross-linking agent.Embodiment 44 and 45 comprises this two kinds of cross-linking agent simultaneously.Compare the tangible reduction of optical haze degree of these embodiment with the eyeglass of making by independent a kind of cross-linking agent.But modulus and percentage elongation have been subjected to passive influence (may be because the too high cause of amount of cross-linking agent).

Embodiment 48-52

Use the formulation reactant mixture shown in the table 8, the mixture of wherein using 72.5% tert-pentyl alcohol and 27.5%PVP (Mw=2500) is as diluent.Reactant mixture is put in the thermoplasticity contact lens mould, and used the irradiation of Philips TL20W/03T fluorescent light bulb, temperature is 45 ℃, and intensity is 0.8mW/cm², shone about 32 minutes.Open mould, within 20 minutes, eyeglass is discharged in 95 ℃ the deionized water.Then eyeglass was inserted in the BBS solution 60 minutes and 122 ℃ of following hot-pressing processing 30 minutes.The performance of gained eyeglass is shown in table 8.

Table 8

Embodiment	48	49	50	51	52	53	54
								Component
SiGMA	30	30	30	33	34	25	20
								PVP	6	6	6	6	7	6	6
DMA	31	31	31	30	30	31	31
								MPDMS	19	22	23.5	16.5	19	25	28
AcPDMS (n＝10)	2	0	0	3	0	0	0
								HEMA	9.85	8.5	6.95	9	6	10.5	12.5
Norbloc	1.5	1.5	1.5	2	1.5	1.5	1.5
								CGI 819	0.23	0.23	0.25	0.48	0	0.23	0.23
CGI 1850	0	0	0	0	1	0	0
								EGDMA	0.4	0.75	0.8	0	0	0.75	0.75
TEGDMA	0	0	0	0	1.5	0	0
								Blue HEMA	0.02	0.02	0	0	0	0.02	0.02
								The % diluent	40.0	40.0	27.3	39.4	25.9	40	40
Diluent is formed	A	A	B	C	D	A	A
								Performance
EWC(％)	45	45	47	49	47	49	50
								DCA (advancing)	52(2)	51(7)	74(10)	108	75(6)	47(2)	58(11)
Modulus (psi)	91	77	69	55	49	63	67
								Percentage elongation (%)	NT	232	167	275	254	110	124
Dk(barrers)	54	60	78	44	87	59	60

Diluent (weight portion):

A=72.5% tert-pentyl alcohol and 27.5%PVP (Mw=2500)

The B=tert-pentyl alcohol

The TMP/2M2P/PVP of C=15/38/38% (Mw=2500)

The 2M2P/TMP of D=57/43

The NT=not test (N.T.)

Therefore, embodiment 48,51 shows, the silicon hydrogel compositions display that comprising the prescription of hydrophilic (EGDMA or TEGDMA) and hydrophobicity cross-linking agent (acPDMS) simultaneously provides goes out excellent performance balance, comprises good water content, moderate Dk, wettability, modulus and percentage elongation.

Embodiment 55

Eyeglass to embodiment 48 carries out clinical evaluation.Described eyeglass is worn usefulness by 18 patients, wears (excision in evening) daytime, and the persistent period was 1 week.During 1 week, its PLTF-NIBUT is 8.4 (± 2.9) seconds, by contrast, concerning ACUVUE  2 eyeglasses, is 7.0 (± 1.3) seconds.For the test eyeglass, there is 97% patient that the surface deposits classification of front is not being had to slight one-level, and for control lenses, has 89%.For test and control lenses, both mobilitys all are acceptable.

Embodiment 56

Eyeglass to embodiment 49 carries out clinical evaluation.Described eyeglass is worn usefulness by 18 patients, wears (excision in evening) daytime, and the persistent period was 1 week.During 1 week, its PLTF-NIBUT is 8.4 (± 2.9) seconds, by contrast, concerning ACUVUE  2 eyeglasses, is 7 (± 1.3) seconds.To the test eyeglass, have 95% patient with the surface deposits classification of front not having to slight one-level, then have 89% for control lenses.For test and control lenses, both mobilitys all are acceptable.

Embodiment 57

Eyeglass to embodiment 51 carries out clinical evaluation.Described eyeglass is worn usefulness by 13 patients, wears (excision in evening) daytime, and the persistent period was 1 week.During 1 week, its PLTF-NIBUT is 4.3 (± 1.9) seconds, by contrast, concerning ACUVUE  2 eyeglasses, is 9.6 (± 2.1) seconds.For the test eyeglass, have 70% patient with the surface deposits classification of front not having to slight one-level, then have 92% for control lenses.For test and control lenses, both mobilitys all are acceptable.Therefore, (concerning embodiment 51 is 108 degree at contact angle test, concerning embodiment 48 is 52 degree) and the clinical wettability (concerning embodiment 51 is 4.3 seconds, is 8.4 seconds concerning embodiment 48) measured by PLTF-NIBUT between exist some association.

Embodiment 58-68

Use listed component of table 9 and following method to make silicone hydrogel lens:

Each component is mixed the formation reactant mixture in container.The container that will contain reactant mixture places also to roll on the jar mill roller and spends the night.

Reactant mixture is placed vacuum desiccator, removed oxygen in 40 minutes by applying vacuum.With exsiccator backfill nitrogen.In the glove box of nitrogen purging, join the recessed antecurvature side of TOPAS  mould cavity by lens materials and obtain contact lens about 0.10g degassing.Second half closing molding with polypropylene convex basis bending mould.Under nitrogen purging, carry out polymerization, use 5mW/cm with the 20W fluorescence generation of TL-03 phosphor²Visible light carries out light-initiated.After 45 ℃ solidify 25 minutes down, open mould.The preceding bight portion that lens mold is recessed is put into the ultra sonic bath (Aquasonic, model is 75D) that contains deionized water, and the condition of ultra sonic bath (amount of temperature and Tween) is as shown in table 10.The eyeglass demould time is shown in table 10.Limpid and the shape of eyeglass is suitable for as contact lens.

Table 9

	Embodiment 58	Embodiment 59	Embodiment 60	Embodiment 61
					SiGMA	3.05	3.2	3.2	3.0
MPDMS	1.7	1.7	1.7	1.7
					DMA	3.2	3.0	3.1	3.2
PVP	0.6	0.6	0.6	0.6
					HEMA	1.0	0.8	0.8	1.0
TEGDMA	0.2	0.4	0.3	0.2
					Norblock	0.15	0.2	0.2	0.2
1850	0.1	0.1	0.3	0.3
					Trigllde	1.5	1.5		1.5
2M2P	2.5	2.5	2.5	2.5
					PVP is low	0.5	1.5	1.5	0.5

Table 10

Embodiment	Preceding embodiment	【Tween】(ppm)	Temperature (℃)	Demould time (min)
					62	58	850	75	10
63	58	10,000	70	10-15
					64	58	0	75	20-22
65	58	850	22	10-15
					66	59	850	85	3
67	60	850	85	8
					68	61	850	75	18

Embodiment 69

The eyeglass of embodiment 59 that will the demoulding in embodiment 66 under 65 ℃ in deionized water further aquation 20 minutes.Then eyeglass is transferred in the BBS solution and made its balance at least about 24 hours.Limpid and its shape of eyeglass is suitable for as contact lens.The water content of eyeglass is 43%, and modulus is 87psi, and percentage elongation is 175%, and Dk is 61barrier.The advancing contact angle of eyeglass is 57 degree.This shows that eyeglass does not contain hydrophobe in fact.

Embodiment 70

The preceding bight portion that the lens mold of embodiment 61 is recessed places about 75 ℃ containing in the ultra sonic bath (Aquasonic, model is 75D) of about 5%DOE-120 at deionized water, eyeglass from frame the demoulding with 18 minutes.

Embodiment 71 (with an organic solvent)

The preceding bight portion that the lens mold of embodiment 61 is recessed places about 75 ℃ containing in the ultra sonic bath (Aquasonic, model is 75D) of about 10%2-propanol organic solvent at deionized water, eyeglass from frame the demoulding with 15 minutes.When Tween was used as additive (embodiment 68), demould time was 18 minutes.Therefore, this embodiment shows that organic solvent also can be used for making the eyeglass demoulding that contains the low-molecular-weight hydrophilic polymer.

Embodiment 72 (not comprising low-molecular-weight PVP)

Use prescription and the method for embodiment 58 to make silicone hydrogel lens, but wherein do not contain any low-molecular-weight PVP.Use following method with the eyeglass demoulding.

The preceding bight portion that lens mold is recessed places about 65 ℃ containing in the ultra sonic bath (Aquasonic, model is 75D) of about 850ppm Tween at deionized water, and eyeglass does not discharge from mould.Under similar demoulding condition (embodiment 62-850ppm Tween and 75 ℃), for the prescription that contains the low-molecular-weight hydrophilic polymer (embodiment 58), demould time is 10 minutes.Therefore, this embodiment shows, does not comprise in prescription in this prescription of low-molecular-weight hydrophilic polymer, only can not finish the demoulding in water.

Embodiment 73

The preceding bight portion that the lens mold of embodiment 72 is recessed places about 75 ℃ containing in the ultra sonic bath (Aquasonic, model is 75D) of about 10%2-propanol organic solvent at deionized water, and the used time of eyeglass demoulding from frame is 20-25 minute.Therefore, use the aqueous solution that contains organic solvent can make the eyeglass demoulding of the present invention that does not comprise the low-molecular-weight hydrophilic polymer.

Embodiment 74-76

According to embodiment 49 preparation prescription, but be to use the light triggers (0.23,0.38 or 0.5wt%) of different amounts, with Philips TL20W/03T fluorescent light bulb (similar output with the spectrum that is used for the visible light that gelling time measures is complementary) with 2.0mW/cm²Intensity irradiation mould, it is solidified down at 45 ℃.The advancing contact angle of gained eyeglass is shown in table 11.

Table 11

Embodiment	Wt％	DCA advances	Gelling time (sec)
				74	0.23	59(4)	65
75	0.38	62(6)	57
				76	0.5	80(7)	51

Embodiment 77-79

At 45 ℃ and 1.0,2.5 and 5.0mW/cm²Measure the gelling time of embodiment 1 prescription down, the results are shown in table 12.

Table 12

Embodiment	Intensity (mW/cm2)	Gelling time (sec)
			77	1	52
78	2.5	38
			79	5	34

The result of embodiment 74-76 and 77-79 is compared with embodiment 27-35, show that when gelling time increased, wettability was improved.Therefore, can use gel point to cooperate contact angle test to determine the suitable condition of cure of given polymer formulators and photoinitiator system.

Embodiment 80 (preparation of macromonomer)

At ambient temperature with nitrogen protection under; add two (dimethylamino) methyl-monosilane (water scavenger) of 30.0g (0.277mol) and the solution of several materials of the following stated in the drying receptacle in being in drying baker: 13.75ml concentration is the TBACB solution (386.0gTBACB is among 1000 milliliters of exsiccant THF) of 1M; 61.39g (0.578mol) xylol; 154.28g (1.541mol) methyl methacrylate (with respect to 1.4 equivalents of initiator), 1892.13g (9.352mol) methacrylic acid 2-(trimethylsiloxy) ethyl ester (with respect to 8.5 equivalents of initiator) and 4399.78g (61.01mol) THF.This mixture joins in the exsiccant three neck round-bottomed flasks that thermocouple and condenser are housed, and all these all are connected on the nitrogenous source.

In stirring with in, starting mixt is cooled to 15 ℃ with nitrogen purging.When solution reaches after 15 ℃, 191.75g (1.100mol) 1-trimethylsiloxy-1-methoxyl group-2-metering system (1 equivalent) is injected in the reactor.Allowing reaction temperature rising to about 62 ℃, is 30ml concentration whole being metered in the residue that reacts of 154.4gTBACB (it is among 11 milliliters of exsiccant THF) of 0.40M then.Reach after 30 ℃ in reaction temperature, begin to be metered into 467.56g (2.311mol) methacrylic acid 2-(trimethylsiloxy) ethyl ester (with respect to 2.1 equivalents of initiator), 3636.6g (3.463mol) normal-butyl monomethacryloxypropterminated-polydimethylsiloxane (with respect to 3.2 equivalents of initiator), the solution of 3673.84g (8.689mol) TRIS (with respect to 7.9 equivalents of initiator) and 20.0g two (dimethylamino) methyl-monosilane.

Allow this mixture temperature rise to about 38-42 ℃, it is cooled to 30 ℃ then.At that time, add 10.0g (0.076mol) two (dimethylamino) methyl-monosilane, the solution of 154.26g (1.541mol) methyl methacrylate (with respect to 1.4 equivalents of initiator) and 1892.13g (9.352mol) methacrylic acid (2-trimethylsiloxy) ethyl ester (with respect to 8.5 equivalents of initiator) and make mixture once more temperature rise arrive about 40 ℃.Reaction temperature is reduced to about 30 ℃, adds 2 gallons of THF and reduce viscosity.Add 439.69g water, the solution of 740.6g methanol and 8.8 gram (0.068mol) dichloroacetic acid also makes mixture reflux 4.5 hours to remove the trimethylsiloxy protecting group on the HEMA.Remove volatile material then, add toluene and help remove water, reach 110 ℃ up to vapor (steam) temperature.

Reaction flask is maintained about 110 ℃, add the solution of 443g (2.201mol) TMI and 5.7g (0.010mol) dibutyl tin dilaurate.Mixture reaction disappears up to detecting isocyanate peak by IR.Reduction vaporization toluene obtains cream-coloured, anhydrous, the active macromonomer of wax shape.Macromonomer is put in the acetone, and weight ratio is approximately acetone: macromonomer is 2: 1.After 24 hours, add entry, precipitation is separated out macromonomer, and macromonomer filtration and use vacuum drying oven were descended dry 20-30 hour at 45-60 ℃.

Embodiment 81-88

The prescription shown in the use table 12 in filling the glove box of nitrogen uses D30 and/or IPL as diluent preparation feedback mixture.Reactant mixture is put in the thermoplasticity contact lens mould, and used the irradiation of Philips TL20W/03T fluorescent light bulb, temperature is 50 ℃, shines about 60 minutes.Open mould, eyeglass is discharged from IPA, leaching is also transferred in the BBS.The performance of gained eyeglass is shown in table 13.

Table 13

Embodiment	81	82	83	84	85	86	87	88
									Component
Macromonomer	18	18	13	13	13	13	13	11
									MPDMS	23	18	29	28	28	28	28	28
AcPDMS (n＝10)	5	10	3	3	3	5	5	5
									TRIS	14	14	15	15	15	14	13	14
DMA	27	27	28	29	30	30	33	32
									HEMA	5	5	2	2	2	2	2	2
Norbloc	2	2	2	2	2	2	2	2
									PVP K-90	5	5	7	6	5	5	5	5
Blue HEMA	0.02	0.02	0.02	0.02	0.02	0.02	0.02	0.02
									CGI 1850	1	1	1	1	1	1	1	1
									The % diluent	20	20	30	30	30	30	30	30
％D30	60	60	100	100	100	60	100	100
									％IPL	40	40	0	0	0	40	0	0
									EWC(％)	36	32	40	40	39	37	40	38
DCA (advancing)			48	46	45		50	57
									Modulus (psi)	149	268	85	90	91	107	134	129
Percentage elongation (%)	216	149	294	300	290	251	176	209
									Dk(barrers)	89	76	114	100	116	117

Embodiment 89

Eyeglass to embodiment 83 carries out clinical evaluation.Described eyeglass is worn usefulness by 10 patients, wears (excision in evening) daytime, and the persistent period is 30 minutes.To every patient, in eyes, wear the test eyeglass, in the another eyes, wear Bauch ﹠amp; Lomb Purevision eyeglass.In the time of 30 minutes, its PLTF-NIBUT is 7.5 (± 1.6) seconds, by contrast, and Bausch ﹠amp; Lomb Purevision eyeglass is 8.6 (± 1.6) seconds.Compare with 100% of control lenses, have among the patient of service test eyeglass 100% patient with the surface deposits classification of front to not having to slight one-level.For test and control lenses, both mobilitys all are acceptable.Eyeglass of the present invention aspect of performance can with the B﹠amp with plasma spraying layer; The L eyeglass compares favourably.Therefore, this embodiment shows, do not having promptly to demonstrate excellent wetting capacity and anti-deposition capability under the situation of coating by comprising the eyeglass that the macromonomer, high molecular hydrophilic polymer and the compatible components that contain siloxanes form.

Embodiment 90

(2.3ml) joins 27.8g 1 with trifluoromethayl sulfonic acid, in 3-two (hydroxyl butyl) tetramethyl disiloxane and the 204.4g prestox cyclisation tetrasiloxane.The gained solution stirring is spent the night.Add 17.0gNa₂CO₃, and mixture stirring 1 hour.Add about 50ml hexane, mixture stir about 1 hour filters then.The reduction vaporization hexane, and by (being heated to 110 ℃ under 1 millibar the pressure, heating about 1 hour and remove cyclic compound, obtaining the polydimethylsiloxane of hydroxyl butyl end-capping.

In another flask, with the 12.2g average equivalent 500 CH₂The end capped Fluorolink  of OH polymer modifiers D10 (Ausimont USA is with Fomblin  ZDOL equivalence) mixes with the 11.8mg dibutyl tin dilaurate.Gained solution is pumped to about 20 millibar twice, all refills with exsiccant N at every turn₂Add the 5.0ml isophorone diisocyanate and mixture is stirred under N2 and spend the night, obtain limpid sticky product.

The polydimethylsiloxane of the above-mentioned 47.7g hydroxyl butyl end-capping that obtains is combined with 41.3 gram dry toluenes.This solution is mixed with Fluorolink -isophorone diisocyanate product, and the gained mixture stirred under nitrogen spend the night.In about 5 hours, under＜1 millibar, from product, evaporate toluene.Add 3.6g methacrylic acid 2-isocyanatoethyl ester, the gained mixture is at N₂Under stirred 4 days, obtain opaque a little viscous fluid fluorosilicone macromonomer.

Embodiment 91

With the fluorosilicone macromonomer and the 1.12g ethanol of preparation among the 2.60g embodiment 90,1.04gTRIS, 1.56g DMA, 32mg Darocur 1173 mixes, and obtains vaporific a little blend, wherein contains 18% diluent (ethanol).In mould of plastics (Topas ), make contact lens by this blend, wherein at room temperature, at N₂In the atmosphere, under fluorescent ultraviolet lamp, solidified 30 minutes.Open mould, eyeglass is discharged (demoulding) in ethanol.At room temperature, use CH₂Cl₂, be IPA about 30 minutes then to each eyeglass leaching, put in the BBS about 2 hours then, afterwards 121 ℃ of following hot-pressing processing 30 minutes.The gained eyeglass is clamminess when touching, and the tendency of clinging is each other arranged.Measure the DCA and be shown in table 14 of advancing of these eyeglasses.

Embodiment 92-98

Use the reactive component (it is measured in reactive component) shown in the table 14, with D30 as diluent preparation feedback mixture.The amount of D30 is in the total amount of reactive component and diluent.Use method preparation feedback mixture and the eyeglass of embodiment 91.The gained eyeglass is smooth when touching, and not sticking mutually each other.

Measure the DCA and being shown in the following table 14 of advancing of these eyeglasses.

Table 14

Embodiment	92	93	94
				Component (wt%)
The fluorosilicone macromonomer	49.7	28.5	19
				TRIS	19.9	0	0
DMA	29.8	24.8	24.7
				PVP(K90)	0	5	4.9
SiGMA	0	40.7	50.1
				EGDMA	0	0.4	0.6
Darocur 1173	0.6	0.6	0.6
				Diluent	Ethanol	D30	D30
The % diluent is in final mixture	18	18	18
DCA advances	132(8)	69(7)	59(9)

Embodiment 92-94 clearly illustrates that, hydrophilic polymer can be used for improving wettability.In these embodiments, contact angle reduces about 50% (embodiment 93)-Yue 60% (embodiment 94) at most.The compositions that contains relatively large fluorosilicone macromonomer and hydrophilic polymer can also be by carrying out functionalized to the silicone macromonomer so that it comprises that reactive hydrogen prepares.

Embodiment 95-99

Use the reactive component shown in the table 15, the tert-pentyl alcohol of 29% (in the total amount of all reactive component and diluent) is as PVP 2,500 (in reactive component) the preparation feedback mixture of diluent and 11%.Shown consumption is based on 100% reactive component.Reactant mixture is put in the thermoplasticity contact lens mould, and used Philips TL20W/03T fluorescent light bulb to shine under nitrogen, temperature is 60 ℃, and intensity is 0.8mW/cm², shone about 30 minutes.Open mould, within 15 minutes, eyeglass is discharged in 95 ℃ the deionized water.Then eyeglass is put in the BBS solution 60 minutes, and 122 ℃ of following hot-pressing processing 30 minutes.The performance of gained eyeglass is shown in table 15.

Table 15

Embodiment	95	96	97	98	99
						Component
SiGMA	30	30	30	30	30
						PVP	0	1	3	6	8
DMA	37	36	34	31	29
						MPDMS	22	22	22	22	22
HEMA	8.5	8.5	8.5	8.5	8.5
						Norbloc	1.5	1.5	1.5	1.5	1.5
CGI 819	0.25	0.25	0.25	0.25	0.25
						EGDMA	0.75	0.75	0.75	0.75	0.75
Performance
						DCA (advancing)	122(8)	112(6)	66(13)	58(8)	54(3)
Mist degree	18(4)	11(1)	13(1)	14(2)	12(1)

Table 15 shows, adds PVP and can significantly reduce contact angle.When only adding 1%, it is about 10% that dynamic contact angle just reduces, and when only adding 3%, dynamic contact angle reduces about 50%.These improve with to the observed result of macromonomer based polyalcohol, consistent such as the result among the embodiment 92-94.

Embodiment 100

The preparation of mPDMS-OH (being used for embodiment 3)

With 96g Gelest MCR-E11 (single-(2, the 3-glycidyl)-the end capped polydimethylsiloxane of propyl ether (molecular weight is 1000)), 11.6g methacrylic acid, 0.10g triethylamine and 0.02g Hydroquinone monomethylether mix and under agitation be heated to 140 ℃ with air bath, be 2.5 hours heat time heating time.Use saturated NaHCO₃Aqueous solution and CH₂Cl₂Extraction product.CH₂Cl₂Layer Na₂SO₄Dry and evaporation obtains the 94g product.HPLC/MS result is consistent with the structure of hope:

Claims (128)

1. wettable silicon hydrogel, it comprises at least a macromonomer or the prepolymer that contains siloxanes; At least a high molecular hydrophilic polymer; Product with at least a compatible components.

2. the hydrogel of claim 1, the wherein said amount that contains the macromonomer of siloxanes is 5wt%-50wt%.

3. the hydrogel of claim 1, wherein containing the macromonomer of siloxanes or the amount of prepolymer is 10wt%-50wt%.

4. the hydrogel of claim 1, wherein containing the macromonomer of siloxanes or the amount of prepolymer is 15wt%-45wt%.

5. the hydrogel of claim 1, the wherein said at least a macromonomer that contains siloxanes comprises at least one siloxane group, with at least one second kind of group, described second kind of group is selected from urethane groups, alkylidene, alkylene oxide base, polyoxyalkylenes, arlydene, Arrcostab, amide groups, carbamate groups, perfluoro alkoxy, NCO and its combination.

6. the hydrogel of claim 5, the wherein said at least a macromonomer that contains siloxanes forms by making described siloxane group and at least a acrylic acid or methacrylic compound polymerization.

7. the hydrogel of claim 5, the wherein said at least a macromonomer that contains siloxanes is selected from methacrylate functionalized silicone-fluoro-ether urethane macromonomer, methacrylate functionalized silicone urethane macromonomer, the prepolymer that the styrene of the methacrylate of hydroxy functional groups and silicone methacrylate is functionalized, and the functionalized polydimethylsiloxane of vinyl carbamate.

8. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 1wt%-15wt%.

9. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 3wt%-15wt%.

10. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 5wt%-12wt%.

11. the silicon hydrogel of claim 14, wherein said hydrophilic polymer is selected from polyamide, polylactone, and polyimides, poly-lactam, functionalized polyamide, functionalized polylactone, functionalized polyimides, functionalized poly-lactam, and composition thereof.

12. the silicon hydrogel of claim 14, wherein said hydrophilic polymer is selected from the poly-N-vinyl ketopyrrolidine, poly-N-vinyl-2-piperidones, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidones, poly-N-vinyl-4-methyl-2-piperidones, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-Pyrrolidone, polyvinyl imidazol, poly--N,N-DMAA, polyvinyl alcohol, polyacrylic acid, polyethylene glycol oxide, poly--2-ethyl- azoles quinoline, the heparin polysaccharide, polysaccharide, its mixture and copolymer.

13. the hydrogel of claim 1, wherein the high molecular hydrophilic polymer is the poly-N-vinyl ketopyrrolidine.

14. the silicon hydrogel of claim 1, wherein said compatible components are the chemical compounds of formula I or II:

Wherein: n is the integer between the 3-35,

R¹Be hydrogen, C_1-6Alkyl;

R², R³And R⁴Be C independently_1-6Alkyl, three C_1-6Alkyl siloxy, phenyl, naphthyl, the C of replacement_1-6Alkyl, the phenyl of replacement, the perhaps naphthyl of Qu Daiing,

Wherein alkyl substituent is selected from the one or more members in the group of being made up of the following stated: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl, wherein aromatic substituent is selected from the one or more members in the group of being made up of the following stated: C_1-6Alkoxy carbonyl, C_1-6Alkyl, C_1-6Alkoxyl, amide groups, halogen, hydroxyl, carboxyl, C_1-6Alkyl-carbonyl and formoxyl,

R⁵Be hydroxyl, contain the alkyl of one or more hydroxyls, perhaps (CH₂(CR⁹R¹⁰)_yO)_x)-R¹¹, wherein y is 1-5, x is the integer of 1-100; R⁹-R¹¹Be independently selected from H, have the alkyl of maximum 10 carbon atoms and the alkyl that is replaced by at least one polar functional group with maximum 10 carbon atoms;

R⁶It is the divalent group that contains maximum 20 carbon atoms;

R⁷It is the univalent perssad that can carry out maximum 20 carbon atoms of containing of free radical or cationic polymerization; With

R⁸Be bivalence or the trivalent group that contains maximum 20 carbon atoms.

15. the silicon hydrogel of claim 1, wherein said compatible components is the monomer that contains silicone of hydroxy-functional, the monomer that contains silicone of described hydroxy-functional is selected from the acrylic acid 2-methyl of 2--2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-[trimethyl silyl) oxygen] the disiloxane base] propoxyl group] propyl ester, (3-methacryloxypropyl-2-hydroxyl propoxyl group) propyl group three (trimethylsiloxy) silane, two (trimethylsiloxy) methyl-monosilanes of (2-methacryloxypropyl-3-hydroxyl propoxyl group) propyl group and composition thereof.

16. the hydrogel of claim 1, wherein said compatible components comprises the chemical compound of at least a formula III:

IWA-HB-[IWA-HB]_x-IWA

Wherein x is 1-10;

IWA is that number-average molecular weight is 1000-50, and 000 daltonian difunctional hydrophilic polymer and HB are the difunctional segments that contains at least one N that can form hydrogen bond.

17. the hydrogel of claim 16, wherein said IWA derived from alpha, ω-hydroxy-end capped PVP and α, ω-hydroxy-end capped polyoxyalkylene glycol.

18. the hydrogel of claim 16, wherein HB is the difunctional group that is selected from amide, acid imide, carbamate, urea and combination thereof.

19. the hydrogel of claim 1, the amount of wherein said compatible components are 5-90wt%.

20. the hydrogel of claim 1 except the described macromonomer or prepolymer that contains siloxanes, further comprises the permeable component of at least a oxygen.

21. the hydrogel of claim 20, the permeable component of wherein said oxygen is selected from the amide analogue of 3-methacryloxypropyl three (trimethylsiloxy) silane; Siloxanes vinyl carbamate analog, siloxanes vinyl carbonate analog and contain siloxanyl monomers, its combination and oligomer.

22. the hydrogel of claim 20, the permeable component of wherein said oxygen are selected from 3-methacryloxypropyl three (trimethylsiloxy) silane, the end capped polydimethylsiloxane of monomethacryloxypropterminated, polydimethylsiloxane, two (trimethylsiloxy) methyl-monosilanes of 3-methacryloxypropyl, methacryloxypropyl pentamethyl disiloxane and combination thereof.

23. the hydrogel of claim 20, the amount of the permeable component of wherein said oxygen is 0-80wt%.

24. the hydrogel of claim 20, the amount of the permeable component of wherein said oxygen is 5-60wt%.

25. the hydrogel of claim 20, the amount of the permeable component of wherein said oxygen is 10-40wt%.

26. the hydrogel of claim 1 further comprises at least a hydrophilic monomer.

27. the hydrogel of claim 26, wherein said at least a hydrophilic monomer comprises at least one acrylic acid groups, vinyl or its combination.

28. the hydrogel of claim 27, the chemical formula of wherein said acrylic acid groups are CH₂=CRCOX, wherein R is hydrogen or C_1-6Alkyl, X are O or N.

29. the hydrogel of claim 26, wherein said at least a hydrophilic monomer is selected from N,N-DMAA, methacrylic acid 2-hydroxyl ethyl ester, the glycerol methacrylate, the 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, the N-vinyl pyrrolidone, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, the N-vinyl formamide, hydrophilic ethylene carbonate monomer, vinyl carbamate monomer, hydrophilic  oxazolone monomer, dextrosan glycosides, and copolymer, and combination.

30. the hydrogel of claim 26, wherein said at least a hydrophilic monomer comprise how pure at least a polyoxyethylene is, the many alcohol of this polyoxyethylene contain the terminal hydroxy groups that one or more functional groups that contained the energy polymerisable double bond replace.

31. the hydrogel of claim 26, wherein said at least a hydrophilic monomer is selected from Polyethylene Glycol, the alkyl polyglucoside of ethoxylation and contain how alcohol of polyethylene that one or more ends that are bonded on the many alcohol of polyethylene can polymeric olefin group.

32. the hydrogel of claim 26, wherein said at least a hydrophilic monomer is selected from N, the N-DMAA, methacrylic acid 2-hydroxyl ethyl ester, glycerol methacrylate, 2-hydroxyethyl methacrylamide, the N-vinyl pyrrolidone, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid and combination thereof.

33. the hydrogel of claim 26, wherein said at least a hydrophilic monomer comprises N,N-DMAA.

34. the hydrogel of claim 26, the amount of wherein said at least a hydrophilic monomer are 0-70wt%.

35. the hydrogel of claim 26, the amount of wherein said at least a hydrophilic monomer are 5-60wt%.

36. the hydrogel of claim 26, the amount of wherein said at least a hydrophilic monomer are 10-50wt%.

37. the hydrogel of claim 1 comprises the siliceous one monomers of the hydroxy-functional of the high molecular hydrophilic polymer of 1-15wt% and 5-90wt%.

38. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 1wt%-15wt%; The compatible components of 5-90wt%; The described macromonomer that contains siloxanes of 5-50wt%, the hydrophilic monomer that contains siloxanyl monomers and 0-70wt% of 0-80wt%.

39. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 3wt%-15wt%; The compatible components of 10-80wt%; Described macromonomer or the prepolymer that contains siloxanes of 10-50wt%, the monomer that contains siloxanes of 5-60wt% and the hydrophilic monomer of 5-60wt%.

40. the hydrogel of claim 1 comprises the high molecular hydrophilic polymer of 5wt%-12wt%; The compatible components of 15-55wt%; The described macromonomer that contains siloxanes of 15-45wt%, the hydrophilic monomer of permeable component of the oxygen of 10-40wt% and 10-50wt%.

41. the hydrogel of claim 14, wherein said y is 1-3, and x is the integer of 2-90.

42. the hydrogel of claim 14, wherein said x are the integers of 10-25.

43. what the hydrogel of claim 1, the amount of wherein said high molecular hydrophilic polymer were enough to make the goods that formed by described hydrogel advances dynamic contact angle than the hydrogel that does not have described hydrophilic polymer low at least 10%.

44. the hydrogel of claim 1, wherein said hydrogel are to connect network or partly connect network.

45. a silicon hydrogel contact lens, it comprises the hydrogel of claim 1, and wherein said contact lens does not carry out surface modification.

46. the eyeglass of claim 45, wherein contact lens is soft adherent lens.

47. the eyeglass of claim 45, the dynamic contact angle that advances of wherein said eyeglass are lower than 70 degree.

48. the eyeglass of claim 45, the dynamic contact angle that advances of wherein said eyeglass are lower than 60 degree.

49. the eyeglass of claim 45, wherein said eyeglass are after wearing with one day, its tear film splitting time is at least 7 seconds.

50. the eyeglass of claim 45, wherein said eyeglass further comprises the modulus that is lower than 90psi.

51. the eyeglass of claim 45, wherein said eyeglass further comprises the water content of 10-60wt%.

52. method, its reactive component that comprises the steps: that (a) will contain at least a compatible components of at least a high molecular hydrophilic polymer, at least a macromonomer that contains siloxanes and effective dose mix and (b) product of curing schedule (a) to form bio-medical instrument.

53. the method for claim 52, wherein said bio-medical instrument comprises Ophthalmoligic instrument.

54. the method for claim 52, wherein said Ophthalmoligic instrument are the silicon hydrogel contact lenss.

55. mixing, the method for claim 52, wherein said reactive component form reactant mixture in the presence of diluent.

56. the method for claim 55, wherein said diluent is selected from ether, ester, alkane, halogenated alkane, silane, amide, alcohol and composition thereof.

57. the method for claim 55, wherein said diluent is selected from amide, alcohol and composition thereof.

58. the method for claim 55, wherein said diluent is selected from oxolane, ethyl acetate, methyl lactate, isopropyl lactate, dichloromethane, prestox cyclisation tetrasiloxane, dimethyl formamide, dimethyl acetylamide, the dimethyl propylene amide, N-Methyl pyrrolidone, the mixture of its mixture and above-mentioned any one and at least a alcohol.

59. the method for claim 55, wherein said diluent comprise at least a alcohol with at least 4 carbon atoms.

60. the method for claim 55, wherein said diluent comprise at least a alcohol with at least 5 carbon atoms.

61. the method for claim 55, wherein said diluent are inert and are easy to the water replacement.

62. the method for claim 55, wherein said diluent comprise at least a tert-butyl alcohol that is selected from, tert-pentyl alcohol, 2-butanols, 2-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 3-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, 3, the alcohol of 7-dimethyl-3-capryl alcohol and composition thereof.

63. the method for claim 55, wherein said diluent is selected from hexanol, enanthol, capryl alcohol, nonyl alcohol, decanol, the tert-butyl alcohol, 3-methyl-3-amylalcohol, isopropyl alcohol, tert-pentyl alcohol, ethyl lactate, methyl lactate, isopropyl lactate, 3,7-dimethyl-3-capryl alcohol, dimethyl formamide, dimethyl acetylamide, dimethyl propylene amide, N-Methyl pyrrolidone and its mixture.

64. the method for claim 55, wherein said diluent are selected from 1-ethyoxyl-2-propanol, 1-methyl-2-propanol, tert-pentyl alcohol, the tripropylene glycol methyl ether, isopropyl alcohol, 1-Methyl-2-Pyrrolidone, N, N-dimethyl propylene amide, ethyl lactate, dipropylene glycol methyl ether and composition thereof.

65. the method for claim 55, the amount of wherein said diluent is for to be lower than 40wt% in reactant mixture.

66. the method for claim 55, the amount of wherein said diluent are between the reactant mixture 10-30wt%.

67. the method for claim 55, wherein said diluent is water miscible under processing conditions, described method comprises that further (c) removes described eyeglass and (d) with described eyeglass aquation from the solidified mould of described eyeglass, wherein step (c) and (d) all carry out in as the aqueous solution of key component comprising water.

68. the method for claim 55, wherein said curing by heating, be exposed under the radiation or it makes up and carries out, and described reactant mixture further comprises at least a initiator.

69. the method for claim 68, wherein said curing is undertaken by the radiation that comprises ionization and/or actinic radiation, and described initiator comprises at least a light trigger.

70. the method for claim 69, wherein said radiation comprises the light of wavelength 150-800nm, and described initiator is selected from mixture and its mixture of aromatics alpha-alcohol ketone, alkoxyl oxygen Benzoinum, acetophenone, acylphosphine oxide, tertiary amine and diketone.

71. the method for claim 69; wherein said initiator is selected from the 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, two (2; 6-dimethoxy benzoyl)-2; 4,4-trimethylphenyl phosphine oxide, two (2; 4; the 6-trimethylbenzoyl)-and phenyl phosphine oxide, 2,4; 6-trimethyl benzyl diphenyl phosphine oxide; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; the benzoic acid methyl ester; the combination of camphorquinone and 4-(N, N-dimethylamino) ethyl benzoate, and composition thereof.

72. the method for claim 69, the amount of wherein said initiator in reactant mixture are in described reactive component 0.1-2wt%.

73. the method for claim 69, wherein said curing is undertaken by visible radiation.

74. the method for claim 73, wherein said initiator comprise 1-hydroxy-cyclohexyl benzophenone, two (2,6-dimethoxy benzoyl)-2,4,4-trimethylphenyl phosphine oxide and composition thereof.

75. the method for claim 73, wherein said initiator comprise two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides.

76. the method for claim 69, wherein said reactive component further comprises at least a ultraviolet absorption compound.

77. the method for claim 73, wherein said curing schedule is 0.1-6mW/cm at solidification intensity²Condition under carry out.

78. the method for claim 73, wherein said curing schedule is 0.2mW/cm at solidification intensity²-3mW/cm²Condition under carry out.

79. the method for claim 77, wherein said curing schedule comprise that further be at least 1 minute hardening time.

80. the method for claim 77, wherein said curing schedule comprise that further be hardening time between 1-60 minute.

81. the method for claim 77, wherein said curing schedule comprise that further be hardening time between 1-30 minute.

82. the method for claim 77, wherein said curing schedule carries out under greater than 25 ℃ temperature.

83. the method for claim 77, wherein said curing schedule carries out under 25 ℃-70 ℃ temperature.

84. the method for claim 77, wherein said curing schedule carries out under 40 ℃-70 ℃ temperature.

85. the method for claim 55, wherein said reactant mixture solidifies in mould, and described method further comprises the step with the demoulding from described mould of described Ophthalmoligic instrument.

86. the method for claim 85, wherein said reactant mixture further comprise at least a low-molecular-weight hydrophilic polymer.

87. the method for claim 86, the number-average molecular weight of wherein said low-molecular-weight hydrophilic polymer is for being lower than 40,000 dalton.

88. the method for claim 86, the number-average molecular weight of wherein said low-molecular-weight hydrophilic polymer is for being lower than 20,000 dalton.

89. the method for claim 86, wherein low-molecular weight polymer is selected from water soluble polyamide, lactams and Polyethylene Glycol, and composition thereof.

90. the method for claim 86, wherein low-molecular weight polymer is selected from polyvinyl pyrrolidone, Polyethylene Glycol, poly--2-ethyl-2- azoles quinoline and composition thereof.

91. the method for claim 86, wherein the amount of low-molecular-weight hydrophilic polymer is in the maximum 20wt% of reactant mixture.

92. the method for claim 86, wherein the amount of low-molecular-weight hydrophilic polymer in reactant mixture between 5-20wt%.

93. the method for claim 86, the wherein said demoulding is carried out with aqueous solution.

94. the method for claim 86, wherein said aqueous solution further comprises at least a surfactant.

95. the method for claim 94, wherein said surfactant comprises at least a nonionic surfactant.

96. the method for claim 94, wherein said surfactant comprises TWEEN  or DOE120.

97. the method for claim 94, the amount of wherein said surfactant is maximum 10,000ppm.

98. the method for claim 94, the amount of wherein said surfactant is between 100-1200ppm.

99. the method for claim 85, wherein said aqueous solution comprises at least a organic solvent.

100. the method for claim 85, the wherein said demoulding is carried out under the temperature of ambient temperature-100 ℃.

101. the method for claim 85, the wherein said demoulding is carried out under 70 ℃-95 ℃ temperature.

102. the method for claim 85, the wherein said demoulding is carried out with stirring.

103. the method for claim 85, wherein said stirring comprises ultrasonication.

104. the method for claim 52, wherein said compatible components are not the macromonomers by the hydroxy-functional of group transfer polymerization preparation.

105. method, its reactive component that comprises the steps: that (a) will contain the compatible components of at least a macromonomer, high molecular hydrophilic polymer and the effective dose that contains siloxanes mix and (b) at the product of minimum gelling time or above time point curing schedule (a) to form wettable bio-medical instrument.

106. the method for claim 105, wherein said device is an eyeglass.

107. the method for claim 106, wherein said device is a contact lens.

108. the method for claim 106, the dynamic contact angle that advances of wherein said eyeglass are 80 degree or lower.

109. the method for claim 106, the dynamic contact angle that advances of wherein said eyeglass are 70 degree or lower.

110. the method for claim 106, the tear film splitting time of wherein said eyeglass is at least 7 seconds.

111. the method for claim 106, wherein said reactive component further comprises at least a initiator.

112. the method for claim 111, wherein said curing is undertaken by radiation, and described condition comprises initiator concentration and the solidification intensity that described minimum gelling time effectively is provided.

113. the method for claim 112, the amount of wherein said initiator are in the maximum 1wt% of all reactive components.

114. the method for claim 112, the amount of wherein said initiator is for to be lower than 0.5wt% in all reactive components.

115. the method for claim 112, wherein said curing is undertaken by radiation, and radiant intensity is for being lower than 5mW/cm²

116. the method for claim 112, wherein said gelling time is at least 30 seconds.

117. the method for claim 112, wherein said gelling time is at least 35 seconds.

118. the method for claim 105, wherein said compatible components are not the macromonomers by the hydroxy-functional of group transfer polymerization preparation.

119. the method for claim 105, wherein said reactive component further comprises at least a macromonomer.

120. be used to improve the method for the Ophthalmoligic instrument wettability that forms by reactant mixture, comprise adding at least a at least a compatible components that contains the macromonomer of siloxanes, at least a high-molecular weight hydrophilic polymer and compatible effective dose in described reactant mixture, wherein said compatible components is not the functionalized prepolymer of being made by the methacrylate of hydroxy functional groups of styrene.

121. the method for claim 120, the compatibility index of wherein said compatible components is greater than 0.5.

122. the method for claim 120, the compatibility index of wherein said compatible components is greater than 1.

123. the method for claim 120, wherein said compatible components comprises at least one siloxane group.

124. the method for claim 123, wherein said compatible components further comprises hydroxy functionality, and its Si/OH ratio is lower than 15: 1.

125. the method for claim 123, the Si/OH ratio of wherein said compatible components is 1: 1-10: between 1.

126. one kind contains the ophthalmic lens of silicon hydrogel according to claim 1, it is not carrying out under the surface-treated situation, has at least 7 seconds tear film splitting time.

127. contact lens of silicon hydrogel according to claim 1, it comprises the permeable component of at least a oxygen, at least a compatible components and high molecular hydrophilic polymer, the amount of high molecular hydrophilic polymer are enough to the tear film splitting time that makes that described device had 7 seconds at least after not carrying out wearing under the surface-treated situation with one day.

128. one kind contains the device of the contact lens of silicon hydrogel according to claim 1, surface deposition can not take place in it under the situation of not carrying out surface modification.